Color safe laundry methods employing zwitterionic formulation components

ABSTRACT

The present invention relates to zwitterionic organic catalyst compound bleach systems and methods for using such bleach systems to increase color safety during laundering of fabrics, especially colored fabrics.

This application claims priority under 35 USC 119(e) to provisionalapplication 60/151,174, filed Aug. 27, 1999.

FIELD OF THE INVENTION

The present invention relates to zwitterionic organic catalyst compoundbleach systems and methods for using such bleach systems to provideincreased color safety during laundering of fabrics, especially coloredfabrics. More particularly, this invention relates to bleach systemscomprising zwitterionic, quaternary imine bleach boosting compounds,zwitterionic, quaternary oxaziridinium bleaching species and mixturesthereof, and methods employing such bleach systems in the laundering offabrics, especially colored fabrics.

BACKGROUND OF THE INVENTION

Oxygen bleaching agents have become increasingly popular in recent yearsin household and personal care products to facilitate stain and soilremoval. Bleaches are particularly desirable for their stain-removing,dingy fabric cleanup, whitening and sanitization properties. Oxygenbleaching agents have found particular acceptance in laundry productssuch as detergents, in automatic dishwashing products and in hardsurface cleansers. Oxygen bleaching agents, however, are somewhatlimited in their effectiveness. Some frequently encountereddisadvantages include color damage on fabrics and damage to laundryappliances, specifically rubber hoses these appliances may contain. Inaddition, oxygen bleaching agents tend to be extremely temperature ratedependent. Thus, the colder the solution in which they are employed, theless effective the bleaching action. Temperatures in excess of 60° C.are typically required for effectiveness of an oxygen bleaching agent insolution.

To solve the aforementioned temperature rate dependency, a class ofcompounds known as “bleach activators” has been developed. Bleachactivators, typically perhydrolyzable acyl compounds having a leavinggroup such as oxybenzenesulfonate, react with the active oxygen group,typically hydrogen peroxide or its anion, to form a more effectiveperoxyacid oxidant. It is the peroxyacid compound which then oxidizesthe stained or soiled substrate material. However, bleach activators arealso somewhat temperature dependent. Bleach activators are moreeffective at warm water temperatures of from about 40° C. to about 60°C. In water temperatures of less than about 40° C., the peroxyacidcompound loses some of its bleaching effectiveness.

U.S. Pat. Nos. 5,576,282 and 5,817,614 both to Miracle et al. discloseattempts at developing bleach systems comprising zwitterionic organiccatalyst compounds which are effective in lower temperature waterconditions and are relatively safe on colors. Although the bleachsystems disclosed in this patent provide enhanced color-safety overtraditional organic catalyst bleach systems, such as cationic, organiccatalyst bleach systems examples of which are disclosed in U.S. Pat.Nos. 5,360,568, 5,360,569, 5,370,826 and 5,482,515 all to Madison etal., consumers desire more color-safe bleach products.

A serious disadvantage associated with methods of using conventionalorganic catalysts, examples of which are described in U.S. Pat. Nos.5,360,568, 5,360,569 and 5,370,826 all to Madison et al., and U.S. Pat.Nos. 5,576,282 and 5,817,614, both to Miracle et al., is that suchorganic catalysts are used at too high an in-use concentration. Forexample, the method used in U.S. Pat. No. 5,482,515 describes a methodwherein the oxygen transfer agent (an organic catalyst compound) ispresent from about 0.01 ppm to 300 ppm, with the preferred concentrationrange from 5 ppm to about 100 ppm per liter of medium. Such aconcentration can result in unacceptable color damage to fabric dyes. Inaddition, such a high concentration can lead to too much availableoxygen (“AvO”) consumption, leading to an altered performance profile(i.e., changing the balance between peracid bleaching and organiccatalyst bleaching). It may be possible to increase stain bleachingperformance with increased organic catalyst concentration but only atthe cost of dye damage and at some point the dye damage becomesunacceptable. Accordingly, there is a need to maximize the ratio ofstain bleaching performance to dye damage of the organic catalyst bleachsystems.

In light of the foregoing, it is evident that there still exists a needfor zwitterionic organic catalyst compound bleach systems and laundrymethods employing such zwitterionic organic catalyst compound bleachsystems that provide effective bleaching in lower temperature waterconditions and provide. superior color-safety properties compared to thelaundry methods employing the organic catalyst bleach systems disclosedin the prior art, as discussed above; and there is a need to maximizethe ratio of stain bleaching performance to dye damage of the organiccatalyst bleach systems.

SUMMARY OF THE INVENTION

The present invention fulfills the need discussed above. The presentinvention provides zwitterionic organic catalyst compound bleach systemsand methods for laundering fabrics, especially colored fabrics,employing such bleach systems.

The zwitterionic organic catalyst compounds of the present invention,and bleach systems comprising such zwitterionic organic catalystcompounds provide increased bleaching effectiveness in lower temperaturewash applications while providing improved color safety, resulting inincreased bleaching effectiveness and color safety as compared toconventional zwitterionic and cationic organic catalyst bleach systems.The zwitterionic organic catalyst compound bleach systems of the presentinvention act in conjunction with or without, preferably with,conventional peroxygen bleaching sources to provide the above-mentionedincreased bleaching effectiveness and superior fabric color safety.

More particularly, this invention relates to zwitterionic organiccatalyst compounds such as zwitterionic, quaternary imine bleachboosting compounds, zwitterionic, quaternary oxaziridinium bleachingspecies, bleach systems comprising such zwitterionic organic catalystcompounds and laundry methods employing such bleach systems.

Nonlimiting examples of the benefits provided by the zwitterionicorganic catalyst compounds and bleach systems employing same includesuperior bleaching effectiveness even in lower temperature water, andimproved color safety.

In one aspect of the present invention, a zwitterionic organic catalystbleach system which demonstrates effective bleaching in lower watertemperature and provides a superior color-safety profile compared to theconventional organic catalyst bleach systems is provided.

In accordance with another aspect of the present invention, azwitterionic organic catalyst bleach system comprising one or morezwitterionic organic catalyst compounds, as described hereinafter, inconjunction with or without a peroxygen source is provided.

In accordance with yet another aspect of the present invention, azwitterionic organic catalyst bleach system comprising one or morezwitterionic organic catalyst compounds, as described hereinafter, inconjunction with a peracid is provided.

In accordance with still yet another aspect of the present invention, amethod for laundering a fabric, especially a colored fabric, in need oflaundering comprising contacting the fabric with a laundry solutioncomprising one or more zwitterionic organic catalyst compound bleachsystems described herein is provided.

In accordance with even still yet another aspect of the presentinvention, a bleach system of the present invention as made by theprocess comprising:

a) providing a wash solution; and

b) adding to said wash solution a bleach composition comprising an

amount of zwitterionic organic catalyst compound of the presentinvention such that the resulting concentration of the zwitterionicorganic catalyst compound in said wash solution is from about 0.001 ppmto about 5 ppm, is provided.

Accordingly, it is an object of the present invention to provide:zwitterionic organic catalyst compound bleach systems, which demonstrateimproved performance even in lower temperature water solutions andimproved color safety; and a method for laundering a fabric, especiallya colored fabric, using one or more of the zwitterionic organic catalystcompound bleach systems described herein.

These and other objects, features and advantages of the presentinvention will be recognized by one of ordinary skill in the art fromthe following description and the appended claims.

All percentages, ratios and proportions herein are on a weight basisunless otherwise indicated. All documents cited herein are herebyincorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

The present invention discloses highly useful zwitterionic organiccatalyst compounds, bleach systems comprising such zwitterionic organiccatalyst compounds, and methods for laundering fabrics, especiallycolored fabrics, employing such bleach systems.

The zwitterionic organic catalyst compounds of the present invention,and bleach systems comprising such zwitterionic organic catalystcompounds provide increased bleaching effectiveness in lower temperaturewash applications while providing improved color safety, resulting inincreased bleaching effectiveness and color safety as compared toconventional cationic and zwitterionic organic catalyst bleach systems.The zwitterionic organic catalyst compound bleach systems of the presentinvention act in conjunction with or without, preferably withconventional peroxygen bleaching sources to provide the above-mentionedincreased bleaching effectiveness and superior fabric color safety.

Definitions

“Peroxygen source” as used herein means materials that generateperoxygen compounds, which can include the peroxygen compoundsthemselves. Examples include, but are not limited to, bleach activators,peracids, percarbonate, perborate, hydrogen peroxide, bleach boostingcompounds, and/or bleaching species (e.g., oxaziridiniums).

“Peroxygen compounds” as used herein includes peracids and peroxides(e.g., hydrogen peroxide, alkyl hydroperoxides, etc.

“Peracid” as used herein means a peroxyacid such as peroxycarboxylicacid and/or peroxymonosulfuric acid (tradname OXONE) and their salts.

Zwitterionic Organic Catalyst Compounds

The zwitterionic organic catalyst compounds and bleach systemscomprising such zwitterionic organic catalyst compounds of the presentinvention bleach system preferably are employed in methods forlaundering fabrics, especially colored fabrics, in need of laundering.Such methods typically encompass bleaching a stained substrate,preferably a colored fabric, in an aqueous medium with a peroxygensource and with a zwitterionic organic catalyst compound whose structureis as defined hereinafter wherein the aqueous medium contains activeoxygen from the peroxygen compound from about 0.05 to about 250 ppm perliter of medium, and the zwitterionic organic catalyst compound from0.001 ppm to about 2 ppm, preferably from about 0.01 ppm to about 2 ppm,more preferably from about 0.1 ppm to about 1.5 ppm, and most preferablyfrom about 0.2 ppm to about 1 ppm.

In the bleaching systems of the present invention, when present, themolar ratio of said peroxygen compound to zwitterionic organic catalystcompound is preferably greater than 1:1, more preferably the molar ratioranges from about 30,000:1 to about 10:1, even more preferably fromabout 10,000:1 to about 50:1, yet even more preferably from about5,000:1 to about 100:1, still even more preferably from about 3,500:1 toabout 150:1.

The molar ratio of peroxygen compound to zwitterionic organic catalystcompound does influence the color safety properties of a bleach system.However, the ppm concentration of the zwitterionic organic catalystcompound in the bleach system is the primary factor in establishing thebleach systems' color safety properties.

A product can deliver, for example, in an aqueous medium a 1 ppmconcentration of a zwitterionic organic catalyst compound with amolecular weight of 300, and a 66 ppm concentration of NOBS (35 ppmpernonanoic acid assuming 100% perhydrolysis) and a 66 ppm concentrationof percarbonate (21 ppm hydrogen peroxide) to give a molar ratio ofperoxygen compound to zwitterionic organic catalyst compound of 246:1. Aproduct which delivers 240 ppm of TAED (forming 160 ppm of peracelicacid) and 865 ppm of percarbonate (forming 281 ppm of hydrogen peroxide)gives a molar ratio of peroxygen compound to zwitterionic organiccatalyst of 3142:1. At 0.25 ppm of zwitterionic organic catalystcompound, the molar ratio would be 12568:1.

In addition to the molar ratios of peroxygen compound to zwitterionicorganic catalyst compound, the bleach systems of the present inventioncan be characterized by the molar ratio of a peracid to zwitterionicorganic catalyst compound. Preferably, the molar ratio of peracid tozwitterionic organic catalyst compound is greater than 1:1, morepreferably about 5,000:1 to about 5:1, still even more preferably fromabout 2,000:1 to about 10:1, and even from about 1,000:1 to 15:1.

The preferred molar ratios of peracid to zwitterionic organic catalystcompound vary with the wash conditions. For example, under European washconditions (typically comprising from about 4500 ppm to 5000 ppm ofdetergent components in the wash water), the preferred molar ratio ofperacid to zwitterionic organic catalyst compound is from about 2,000:1to about 150:1. Whereas, under North American wash conditions (typicallycomprising from about 850 ppm to about 1000 ppm of detergent componentsin the wash water), the preferred molar ratio of peracid to zwitterionicorganic catalyst compound is from about 150:1 to about 5:1.

Yet in addition to the molar ratios of peracid to zwitterionic organiccatalyst compound, the bleach system of the present invention can becharacterized by the molar ratio of a hydrophobic peracid tozwitterionic organic catalyst compound, preferably a hydrophobiczwitterionic organic catalyst compound. Preferably the molar ratio ofthe hydrophobic peracid to zwitterionic organic catalyst compound isfrom about 500:1 to about 15:1, more preferably about 350:1 to about20:1, still even more preferably from about 200:1 to about 25:1, andeven more preferably from about 100:1 to about 35:1.

Preferably, the zwitterionic organic catalyst compounds of the presentinvention, more preferably the iminium-based zwitterionic organiccatalyst compounds of the present invention, include, but are notlimited to, bleach boosting compounds.

I. Bleach Boosting Compounds

The bleach boosting compounds, preferably iminium-based bleach boostingcompounds, of the present invention include, but are not limited to,aryliminium zwitterions, which have a net charge of from about +3 toabout −3.

Aryliminium Zwitterions

The aryliminium zwitterions, which have a net charge of from about +3 toabout −3, are represented by the formula [II]:

where R⁵-R⁷ are independently selected from substituted or unsubstitutedradicals selected from the group consisting of H, alkyl, cycloalkyl,aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; alsopresent in this formula is the radical represented by the formula:

—T_(o)—Z_(p) ^(⊖)

where Z_(p) ⁻ is covalently bonded to T_(o), and Z_(p) ⁻ is selectedfrom the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻and p is either 1, 2 or 3; T_(o) is selected from the group consistingof substituted or unsubstituted, saturated or unsaturated alkyl,cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring.

Preferably, the aryliminium zwieterions, which have a net charge of fromabout +3 to about −3, are represented by the formula [XII]:

where m is 1 to 3 when G is present and m is 1 to 4 when G is notpresent; and n is an integer from 0 to 4; each R²⁶ is independentlyselected from a substituted or unsubstituted radical selected from thegroup consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclicring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,keto, carboxylic, and carboalkoxy radicals, and any two vicinal R²⁶substituents may combine to form a fused aryl, fused carbocyclic orfused heterocyclic ring; R²⁵ may be a substituted or unsubstitutedradical selected from the group consisting of H, alkyl, cycloalkyl,alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; alsopresent in this formula is the radical represented by the formula:

—T_(o)—Z_(p) ^(⊖)

where Z_(p) ⁻ is covalently bonded to T_(o), and Z_(p) ⁻ is selectedfrom the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻and p is either 1, 2 or 3; T_(o) is selected from the group consistingof:

wherein q is an integer from 1 to 8; R²⁹ is independently selected fromsubstituted or unsubstituted radicals selected from the group consistingof linear or branched H, alkyl, cycloalkyl, allaryl, aryl, aralkyl,alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl andamide groups; G is selected from the group consisting of: (1) —O—; (2)—N(R³⁰)—; and (3) —N(R³⁰R³¹)—; R²⁷, R²⁸, R³⁰ and R³¹ are substituted orunsubstituted radicals independently selected from the group consistingof H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes,heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups andamide groups; any of R²⁵, R²⁶, R²⁷, R²⁸, R³⁰ and R³¹ may be joinedtogether with any other of R²⁵, R²⁶, R²⁷, R²⁸, R³⁰ and R³¹ to form partof a common ring; any geminal R²⁷-R²⁸ may combine to form a carbonyl;any vicinal R²⁷-R³¹ may join to form unsaturation; and wherein any onegroup of substituents R²⁷-R³¹ may combine to form a substituted orunsubstituted fused unsaturated moiety.

More preferred aryliminium zwitterions, which have a net charge of fromabout +3 to about −3, as represented by the formula [XII], include thoseof formula [XII] where R²⁵ is H or methyl, and for the radicalrepresented by the formula:

—T_(o)—Z_(p) ^(⊖)

Z_(p) ⁻ is —CO₂ ⁻, —SO₃ ⁻ or —OSO₃ ⁻, and p is 1 or 2.

Most preferably, the aryliminium zwitterions are represented by theformula [XIIa]:

wherein R⁴¹-R⁴⁴ may be independently selected from a substituted orunsubstituted radical selected from the group consisting of H, linear orbranched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl, aryl,aralkyl, alkylene, alkoxy,radicals, provided that any of R⁴¹-R⁴⁴ may bejoined together with any other of R⁴¹-R⁴⁴ to form part of a common ring;more preferred, at least one, even more preferably two of R⁴¹-R⁴⁴ is H.Most preferably, R⁴¹ and/or R⁴⁴ is a linear or branched C1-C16 alkyl orcycloalkyl, even more preferably the sum of the carbon atoms within R⁴¹and R⁴⁴ is from 5-15, most preferably 6-13.

II. Bleaching Species

The bleaching species (oxaziridiniums) may also be used directly inaccordance with the present invention. The bleaching species of thepresent invention include, but are not limited to, oxaziridiniumzwitterions, which have a net charge of from about +3 to about −3.

The aryliminium zwitterions of the present invention act in conjunctionwith a peroxygen source, when present, to increase bleachingeffectiveness. Without being bound by theory, it is believed that thearyliminium zwitterions react with the peroxygen source to form a moreactive bleaching species, a zwitterionic quaternary oxaziridiniumcompound, as represented by the following reaction by way of example:

The zwitterionic oxaziridinium compounds can have an increased orpreferred activity at lower temperatures relative to the peroxygencompound.

Oxaziridinium Zwitterions

The oxaziridinium zwitterions, which have a net charge of from about +3to about −3, are represented by formula [IV]:

where R^(5′)-R^(7′) are independently selected from substituted orunsubstituted radicals selected from the group consisting of H, alkyl,cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro,halo, cyano, sulfonato, alkoxy, keto, carboxylic, and carboalkoxyradicals; also present in this formula is the radical represented by theformula:

—T′_(o)—Z′_(p) ^(⊖)

where Z′_(p) ⁻ is covalently bonded to T′_(o), and Z′_(p) ⁻ is selectedfrom the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻and p is either 1, 2 or 3; T′_(o) is selected from the group consistingof substituted or unsubstituted, saturated or unsaturated alkyl,cycloalkyl, aryl, alkaryl, aralkyl, and heterocyclic ring.

Preferably, the oxaziridinium zwitterions, which have a net charge offrom about +3 to about −3, are represented by formula [XIV]:

wherein m is 1 to 3 when G is present and m is 1 to 4 when G is notpresent; and n is an integer from 0 to 4; each R^(26′) is independentlyselected from a substituted or unsubstituted radical selected from thegroup consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclicring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,keto, carboxylic, and carboalkoxy radicals, and any two vicinal R^(26′)substituents may combine to form a fused aryl, fused carbocyclic orfused heterocyclic ring; R^(25′) may be a substituted or unsubstitutedradical selected from the group consisting of H, alkyl, cycloalkyl,alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,sulfonato, alkoxy, keto, carboxylic, and carboalkoxy radicals; and alsopresent in this formula is the radical represented by the formula:

—T′_(o)—Z′_(p) ^(⊖)

where Z′_(p) ⁻ is covalently bonded to T′_(o), and Z′_(p) ⁻ is selectedfrom the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂ ⁻ and —OSO₂⁻, and a is either 1 or 2; T′_(o) is selected from the group consistingof:

wherein q is an integer from 1 to 8; R^(29′) is independently selectedfrom substituted or unsubstituted radicals selected from the groupconsisting of linear or branched H, alkyl, cycloalkyl, alkaryl, aryl,aralkyl, alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyallyland amide groups, provided that all R^(29′) groups are not independentlyselected to be H; G is selected from the group consisting of: (1) —O—;(2) —N(R^(30′))—; and (3) —N(R^(30′)R^(31′))—; R^(27′), R^(28′), R^(30′)and R^(31′) are substituted or unsubstituted radicals independentlyselected from the group consisting of H, oxygen, alkyl, cycloalkyl,alkaryl, aryl, aralkyl, alkylenes, heterocyclic ring, alkoxys,arylcarbonyl groups, carboxyalkyl groups and amide groups; any ofR^(25′), R^(26′), R^(27′), R^(28′), R^(30′) and R^(31′) may be joinedtogether with any other of R^(25′), R^(26′), R^(27′), R^(28′), R^(30′)and R^(31′) to form part of a common ring; any germinal R^(27′)-R^(28′)may combine to form a carbonyl; any vicinal R^(27′)-R^(31′) may join toform unsaturation; and wherein any one group of substituentsR^(27′)-R^(31′) may combine to form a substituted or unsubstituted fusedunsaturated moiety.

More preferred oxaziridinium zwitterions, which have a net charge offrom about +3 to about −3, as represented by the formula [XIV], includethose of formula [XIV] where R^(25′) is H or methyl, and for the radicalrepresented by the formula:

 —T′_(o)—Z′_(p) ^(⊖)

Z′_(p) ⁻ is —CO₂ ⁻, —SO₃ ⁻ or —OSO₃ ⁻, and p is 1 or 2.

Most preferably, the oxaziridinium zwitterions are represented by theformula [XIVa]:

wherein R⁴¹-R⁴⁴ may be independently selected from a substituted orunsubstituted radical selected from the group consisting of H, linear orbranched, substituted or unsubstituted alkyl, cycloalkyl, alkaryl, aryl,aralkyl, alkylene, alkoxy, radicals, provided that any of R⁴¹-R⁴⁴ may bejoined together with any other of R⁴¹-R⁴⁴ to form part of a common ring;more preferred, least one, even more preferably two of R⁴¹-R⁴⁴ is H.Most preferably, R⁴¹ and/or R⁴⁴ is a linear or branched C1-C16 alkyl orcycloalkyl, even more preferably the sum of the carbon atoms within R⁴¹and R⁴⁴ is from 5-15, most preferably 6-13.

Concentration of Organic Catalyst Compounds

The zwitterionic organic catalyst compounds (bleach boosting compoundsand bleaching species) of the present invention may be and preferablyare added to a wash solution, typically aqueous wash solution, in levelsof from about 0.00001% (0.0001 ppm) to about 10% (100 ppm) by weight ofthe composition, and preferably from about 0.0001% (0.001 ppm) to about1% (10 ppm) by weight of the composition, more preferably from about0.001% (0.01 ppm) to about 0.5% (5 ppm), even more preferably from about0.004% (0.04 ppm) to about 0.25% (2.5 ppm). Most preferably from about0.01% (0.1 ppm) to about 0.1% (1 ppm).

The conversion values (in ppm) are provided for exemplary purposes,based on an in-use product concentration of 1000 ppm. A 1000 ppm washsolution of a product containing 0.2% organic catalyst compound byweight results in a organic catalyst compound concentration of 2 ppm.Similarly, a 3500 ppm wash solution of a product containing 0.2% organiccatalyst compound by weight results in a organic catalyst compoundconcentration of 6.5 ppm.

Decomposition of Organic Catalysts

The organic catalysts, specifically the bleach boosting compounds of thepresent invention are susceptible to decomposition by variousdecomposition pathways including, but not limited to, the aromatizationpathway. The aromatization (decomposition) reaction of 6-membered ringboosters is well known in the art, as exemplified, without being limitedby theory, in Hanquet et al., Tetrahedron 1993, 49, pp. 423-438. Othermeans of decomposition include, but are not limited to, attack on thebleach boosting compound and/or on the bleaching species bynucleophiles, including but not limited to attack by hydroxide anion,perhydroxide anion, carboxylate anion, percarboxylate anion and othernucleophiles present under in-wash conditions.

Methods for Delayed (Controlled) Addition of Organic Catalyst Compounds

It has surprisingly been found with organic catalyst compounds oflimited lifetime, that the addition of organic catalyst compounds by adelivery means to a wash solution after a fabric has been added to awash solution, especially a wash solution that contains a peroxygensource, provides enhanced bleaching compared to the addition of suchorganic catalyst compounds to the wash solution before a fabric has beenadded to the wash solution. It is believed, without being limited bytheory, that the organic catalyst compound undergoes decomposition inthe wash solution prior to the introduction of the fabric load. Onemethod for improving the performance of organic catalyst compounds is todelay the addition of the organic catalyst compound of the presentinvention to the wash solution. Another method of improving theperformance of organic catalyst compounds is to use an organic catalystcompound with increased stability to the wash conditions. Methods fordelayed (controlled) addition of organic catalyst compounds are morefully described in copending and co-owned U.S. Provisional PatentApplication Ser. No. 60/151,002 entitled “Controlled Availability ofFormulation Components, Compositions and Laundry Methods Employing Same”filed Aug. 27, 1999.

Bleach Systems Comprising Zwitterionic Organic Catalyst Compounds

In addition to the use of zwitterionic organic catalyst compoundsdiscussed above, the zwitterionic organic catalyst compounds of thepresent invention may be employed in conjunction with or without,preferably with a peroxygen source in other bleach systems, regardlessof their form. For example, the zwitterionic organic catalyst compoundsmay be employed in a laundry additive product. In the bleach systems ofthe present invention, the peroxygen source may be present in levels offrom about 0.1% to about 60% by weight of the composition, andpreferably from about 1% to about 40% by weight of the composition. In acomposition, the organic catalyst compound may be present from about0.00001% to about 10% by weight of the system, and preferably from about0.0001% to about 1% by weight of the system, more preferably from about0.001% to about 0.5%, even more preferably from about 0.004% to about0.25%. Most preferably from about 0.01% to about 0.1%.

The bleach systems of the present invention may be advantageouslyemployed in laundry applications, hard surface cleaning, automaticdishwashing applications, as well as cosmetic applications such asdentures, teeth, hair and skin. However, due to the unique advantages ofincreased color safety and increased effectiveness in cold and possiblywarm water solutions due to possible increased stability, the organiccatalyst compounds of the present invention are ideally suited forlaundry applications such as the bleaching of fabrics through the use ofbleach-containing detergents or laundry bleach additives. Furthermore,the bleach boosting compounds of the present invention may be employedin both granular and liquid compositions.

The zwitterionic organic catalyst compounds and bleach systemscomprising the organic catalyst compounds can be used as antimicrobialagents and disinfectants.

Accordingly, the bleach systems of the present invention may includevarious additional ingredients which are desirable in laundryapplications. Such ingredients include detersive surfactants, bleachcatalysts, builders, chelating agents, enzymes, polymeric soil releaseagents, brighteners and various other ingredients. Compositionsincluding any of these various additional ingredients preferably have apH of from about 6 to about 12, preferably from about 8 to about 10.5 ina 1% solution of the bleach system.

The bleach systems preferably include at least one detersive surfactant,at least one chelating agent, at least one detersive enzyme andpreferably has a pH of about 6 to about 12, preferably from 8 to about10.5 in a 1% solution of the bleach system.

In another embodiment of the present invention, a method for launderinga fabric, especially a colored fabric, in need of laundering isprovided. The preferred method comprises contacting the fabric with alaundry solution. The fabric may comprise most any fabric capable ofbeing laundered in normal consumer use conditions. The laundry solutioncomprises a bleach system comprising one or more zwitterionic organiccatalyst compounds of the present invention, as fully described herein.The water temperatures preferably range from about 0° C. to about 50° C.or higher. The water to fabric ratio is preferably from about 1:1 toabout 15:1.

The laundry solution may further include at least one additionalingredient selected from the group consisting of detersive surfactants,chelating agents, detersive enzymes and mixtures thereof. Preferably,the laundry solution has a pH of about 6 to about 12, preferably fromabout 8 to about 10.5 in a 1% solution of the bleach system.

The bleach systems of the present invention typically and preferablycomprise a peroxygen source. Peroxygen sources are well-known in the artand the peroxygen source employed in the present invention may compriseany of these well known sources, including peroxygen compounds as wellas compounds which under consumer use conditions provide an effectiveamount of peroxygen in situ. The peroxygen source may include a hydrogenperoxide source, the in situ formation of a peracid anion through thereaction of a hydrogen peroxide source and a bleach activator, preformedperacid compounds or mixtures of suitable peroxygen sources. Of course,one of ordinary skill in the art will recognize that other sources ofperoxygen may be employed without departing from the scope of theinvention. Preferably, the peroxygen source is selected from the groupconsisting of:

(i) preformed peracid compounds selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfmric acids and salts, and mixturesthereof, and

(ii) hydrogen peroxide sources selected from the group consisting ofperborate compounds, percarbonate compounds, perphosphate compounds andmixtures thereof, and a bleach activator.

When present, peroxygen sources (peracids and/or hydrogen peroxidesources) will typically be at levels of from about 1%, preferably fromabout 5% to about 30%, preferably to about 20% by weight of thecomposition. If present, the amount of bleach activator will typicallybe from about 0.1%, preferably from about 0.5% to about 60%, preferablyto about 40% by weight, of the bleach system comprising the bleachingagent-plus-bleach activator.

a. Preformed Peracids

The preformed peracid compound as used herein is any convenient compoundwhich is stable and which under consumer use conditions provides aneffective amount of peracid anion. The organic catalysts of the presentinvention may of course be used in conjunction with a preformed peracidcompound selected from the group consisting of percarboxylic acids andsalts, percarbonic acids and salts, perimidic acids and salts,peroxymonosulfuric acids and salts, and mixtures thereof, examples ofwhich are described in U.S. Pat. No. 5,576,282 to Miracle et al.

One class of suitable organic peroxycarboxylic acids have the generalformula:

wherein R is an alkylene or substituted alkylene group containing from 1to about 22 carbon atoms or a phenylene or substituted phenylene group,and Y is hydrogen, halogen, alkyl, aryl, —C(O)OH or —C(O)OOH.

Organic peroxyacids suitable for use in the present invention cancontain either one or two peroxy groups and can be either aliphatic oraromatic. When the organic peroxycarboxylic acid is aliphatic, theunsubstituted peracid has the general formula:

where Y can be, for example, H, CH₃, CH₂Cl, C(O)OH, or C(O)OOH; and n isan integer from 0 to 20. When the organic peroxycarboxylic acid isaromatic, the unsubstituted peracid has the general formula:

wherein Y can be, for example, hydrogen, alkyl, alkylhalogen, halogen,C(O)OH or C(O)OOH.

Typical monoperoxy acids useful herein include alkyl and arylperoxyacids such as:

(i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g.peroxy-a-naphthoic acid, monoperoxyphthalic acid (magnesium salthexahydrate), and o-carboxybenzamidoperoxyhexanoic acid (sodium salt);

(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids,e.g. peroxylauric acid, peroxystearic acid, N-nonanoylaminoperoxycaproicacid (NAPCA), N,N-(3-octylsuccinoyl)aminoperoxycaproic acid (SAPA) andN,N-phthaloylaninoperoxycaproic acid (PAP);

(iii) amidoperoxyacids, e.g. monononylaride of either peroxysuccinicacid (NAPSA) or of peroxyadipic acid (NAPAA).

Typical diperoxyacids useful herein include alkyl diperoxyacids andaryldiperoxyacids, such as:

(iv) 1,12-diperoxydodecanedioic acid;

(v) 1,9-diperoxyazelaic acid;

(vi) diperoxybrassylic acid; diperoxysebacic acid anddiperoxyisophthalic acid;

(vii) 2-decyldiperoxybutane-1,4-dioic acid;

(viii) 4,4′-sulfonylbisperoxybenzoic acid.

Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, Hartman,issued Nov. 20, 1984, U.S. Pat. No. 4,634,551 to Burns et al., EuropeanPatent Application 0,133,354, Banks et al. published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al. issued Nov. 1, 1983. Sources alsoinclude 6-nonylamino-6-oxoperoxycaproic acid as fully described in U.S.Pat. No. 4,634,551, issued Jan. 6, 1987 to Burns et al. Persulfatecompounds such as for example OXONE, manufactured commercially by E.I.DuPont de Nemours of Wilmington, Del. can also be employed as a suitablesource of peroxymonosulfuric acid.

b. Hydrogen Peroxide Sources

The hydrogen peroxide source may be any suitable hydrogen peroxidesource and present at such levels as fully described in U.S. Pat. No.5,576,282. For example, the hydrogen peroxide source may be selectedfrom the group consisting of perborate compounds, percarbonatecompounds, perphosphate compounds and mixtures thereof.

Hydrogen peroxide sources are described in detail in the hereinincorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed(1992, John Wiley & Sons), Vol. 4, pp. 271-300 “Bleaching Agents(Survey)”, and include the various forms of sodium perborate and sodiumpercarbonate, including various coated and modified forms.

The preferred source of hydrogen peroxide used herein can be anyconvenient source, including hydrogen peroxide itself. For example,perborate, e.g., sodium perborate (any hydrate but preferably the mono-or tetra-hydrate), sodium carbonate peroxyhydrate or equivalentpercarbonate salts, sodium pyrophosphate peroxyhydrate, ureaperoxyhydrate, or sodium peroxide can be used herein. Also useful aresources of available oxygen such as persulfate bleach (e.g., OXONE,manufactured by DuPont). Sodium perborate monohydrate and sodiumpercarbonate are particularly preferred. Mixtures of any convenienthydrogen peroxide sources can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with a silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Compositions of the present invention may also comprise as the bleachingagent a chlorine-type bleaching material. Such agents are well known inthe art, and include for example sodium dichloroisocyanurate (“NaDCC”).However, chlorine-type bleaches are less preferred for compositionswhich comprise enzymes.

b. Bleach Activators

Preferably, the peroxygen source in the composition is formulated withan activator (peracid precursor). The activator is present at levels offrom about 0.01%, preferably from about 0.5%, more preferably from about1% to about 15%, preferably to about 10%, more preferably to about 8%,by weight of the composition. A bleach activator as used herein is anycompound which when used in conjunction with a hydrogen peroxide sourceleads to the in situ production of the peracid corresponding to thebleach activator. Various non limiting examples of activators are fullydisclosed in U.S. Pat. Nos. 5,576,282, 4,915,854 and 4,412,934. See alsoU.S. Pat. No. 4,634,551 for other typical bleaches and activators usefulherein.

Preferred activators are selected from the group consisting oftetraacetyl ethylene diamine (TAED), benzoylcaprolactam (BzCL),4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam,benzoyloxybenzenesulphonate (BOBS), nonanoyloxybenzenesulphonate (NOBS),plenyl benzoate (PhBz), decanoyloxybenzenesulphonate (CIO-OBS),benzoylvalerolactam (BZVL), octanoyloxybenzenesulphonate (C₈-OBS),perhydrolyzable esters and mixtures thereof, most preferablybenzoylcaprolactam and benzoylvalerolactam. Particularly preferredbleach activators in the pH range from about 8 to about 9.5 are thoseselected having an OBS or VL leaving group.

Preferred hydrophobic bleach activators include, but are not limited to,nonanoyloxybenzenesulphonate (NOBS), 4-[N-(nonanoyl)aminohexanoyloxy]-benzene sulfonate sodium salt (NACA-OBS) an example ofwhich is described in U.S. Pat. No. 5,523,434,lauroyloxybenzenesulphonate (LOBS or C₁₂-OBS),10-undecenoyloxybenzenesulfonate (UDOBS or C₁₁-OBS with unsaturation inthe 10 position), and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those described in U.S. Pat. No.5,698,504 Christie et al., issued Dec. 16, 1997; U.S. Pat. No. 5,695,679Christie et al. issued Dec. 9, 1997; U.S. Pat. No. 5,686,401 Willey etal., issued Nov. 11, 1997; U.S. Pat. No. 5,686,014 Hartshorn et al.,issued Nov. 11, 1997; U.S. Pat. No. 5,405,412 Willey et al., issued Apr.11, 1995; U.S. Pat. No. 5,405,413 Willey et al., issued Apr. 11. 1995;U.S. Pat. No. 5,130,045 Mitchel et al., issued Jul. 14, 1992; and U.S.Pat. No. 4,412,934 Chung et al., issued Nov. 1, 1983, and copendingpatent applications U.S. Ser. Nos. 08/709,072, 08/064,564, all of whichare incorporated herein by reference.

The mole ratio of peroxygen bleaching compound (as AvO) to bleachactivator in the present invention generally ranges from at least 1:1,preferably from about 20:1, more preferably from about 10:1 to about1:1, preferably to about 3:1.

Quaternary substituted bleach activators may also be included. Thepresent bleach systems preferably comprise a quaternary substitutedbleach activator (QSBA) or a quaternary substituted peracid (QSP); morepreferably, the former. Preferred QSBA structures are further describedin U.S. Pat. No. 5,686,015 Willey et al., issued Nov. 11, 1997; U.S.Pat. No. 5,654,421 Taylor et al., issued Aug. 5, 1997; U.S. Pat. No.5,460,747 Gosselink et al., issued Oct. 24, 1995; U.S. Pat. No.5,584,888 Miracle et al., issued Dec. 17, 1996; and U.S. Pat. No.5,578,136 Taylor et al., issued Nov. 26, 1996; all of which areincorporated herein by reference.

Highly preferred bleach activators useful herein are amide-substitutedas described in U.S. Pat. No. 5,698,504, U.S. 5,695,679, and U. S.5,686,014 each of which are cited herein above. Preferred examples ofsuch bleach activators include:(6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate (6-decanamidocaproyl)oxybenzenesulfonate and mixtures thereof.

Other useful activators, disclosed in U.S. Pat. No. 5,698,504, U.S.5,695,679, U.S. 5,686,014 each of which is cited herein above and U.S.Pat. No. 4,966,723Hodge et al., issued Oct. 30, 1990, includebenzoxazin-type activators, such as a C₆H₄ ring to which is fused in the1,2-positions a moiety —C(O)OC(R¹)═N—.

Depending on the activator and precise application, good bleachingresults can be obtained from bleaching systems having with in-use pH offrom about 6 to about 13, preferably from about 9.0 to about 10.5.Typically, for example, activators with electron-withdrawing moietiesare used for near-neutral or sub-neutral pH ranges. Alkalis andbuffering agents can be used to secure such pH.

Acyl lactam activators, as described in U.S. Pat. No. 5,698,504, U.S.5,695,679 and U.S. 5,686,014, each of which is cited herein above, arevery useful herein, especially the acyl caprolactams (see for example WO94-28102 A) and acyl valerolactams (see U.S. Pat. No. 5,503,639 Willeyet al., issued Apr. 2, 1996 incorporated herein by reference).

d. Organic Peroxides, especially Diacyl Peroxides

In addition to the bleaching agents described above, the bleach systemsof the present invention can optionally include organic peroxides.Organic peroxides are extensively illustrated in Kirk Othmer,Encyclopedia of Chemical Technology, Vol. 17, John Wiley and Sons, 1982at pages 27-90 and especially at pages 63-72, all incorporated herein byreference. If a diacyl peroxide is used, it will preferably be one whichexerts minimal adverse impact on spotting/filming.

e. Metal-containing Bleach Catalysts

The bleach systems can also optionally include metal-containing bleachcatalysts, preferably manganese and cobalt-containing bleach catalysts.

One type of metal-containing bleach catalyst is a catalyst systemcomprising a transition metal cation of defined bleach catalyticactivity, such as copper, iron, titanium, ruthenium tungsten,molybdenum, or manganese cations, an auxiliary metal cation havinglittle or no bleach catalytic activity, such as zinc or aluminumcations, and a sequestrate having defined stability constants for thecatalytic and auxiliary metal cations, particularlyethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof. Suchcatalysts are disclosed in U.S. Pat. No. 4,430,243 Bragg, issued Feb. 2,1982.

i. Manganese Metal Complexes

If desired, the compositions herein can be catalyzed by means of amanganese compound. Such compounds and levels of use are well known inthe art and include, for example, the manganese-based catalystsdisclosed in U.S. Pat. No. 5,576,282 Miracle et al., issued Nov. 19,1996; U.S. Pat. No. 5,246,621 Favre et al., issued Sep. 21, 1993; U.S.Pat. No. 5,244,594 Favre et al., issued Sep. 14, 1993; U.S. Pat. No.5,194,416 Jureller et al., issued Mar. 16, 1993; U.S. Pat. No. 5,114,606van Vliet et al., issued May 19, 1992; and European Pat. App. Pub.Nos.549,271 A1, 549,272 A1, 544,440 A2, and 544,490 A1; Preferredexamples of these catalysts include Mn^(IV)₂(u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂₋(PF₆)₂, Mn^(III)₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₂,Mn^(IV) ₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^(III)Mn^(IV)₄(u-O)₁(u-OAc)₂₋(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃,Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃(PF₆), andmixtures thereof. Other metal-based bleach catalysts include thosedisclosed in U.S. Pat. No. 4,430,243 included by reference herein aboveand U.S. Pat. No. 5,114,611 van Kralingen, issued May 19, 1992. The useof manganese with various complex ligands to enhance bleaching is alsoreported in the following: U.S. Pat. No. 4,728,455 Rerek, issued Mar. 1,1988; U.S. Pat. No. 5,284,944 Madison, issued Feb. 8, 1994; U.S. Pat.No. 5,246,612 van Dijk et al., issued Sep. 21, 1993; U.S. Pat. No.5,256,779 Kerschner et al., issued Oct. 26, 2993; U.S. Pat. No.5,280,117 Kerschner et al., issued Jan. 18, 1994; U.S. Pat. No.5,274,147 Kerschner et al., issued Dec. 28, 1993; U.S. Pat. No.5,153,161 Kerschner et al., issued Oct. 6, 1992; and U.S. Pat. No.5,227,084 Martens et al., issued Jul. 13, 1993.

ii. Cobalt Metal Complexes

Cobalt bleach catalysts useful herein are known, and are described, forexample, in U.S. Pat. No. 5,597,936 Perkins et al., issued Jan. 28,1997; U.S. Pat. No. 5,595,967 Miracle et al., Jan. 21, 1997; U.S. Pat.No. 5,703,030 Perkins et al., issued Dec. 30, 1997; and M. L. Tobe,“Base Hydrolysis of Transition-Metal Complexes”, Adv. Inorg. Bioinorg.Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst usefulherein are cobalt pentaamine acetate salts having the formula[Co(NH₃)₅OAc]T_(y), wherein “OAc” represents an acetate moiety and“T_(y)” is an anion, and especially cobalt pentaantine acetate chloride,[Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂;[Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)₂ (herein“PAC”).

These cobalt catalysts are readily prepared by known procedures, such astaught for example in U.S. Pat. Nos. 5,597,936, 5,595,967, 5,703,030,cited herein above, the Tobe article and the references cited therein,and in U.S. Pat. No. 4,810,410, to Diakun et al, issued Mar. 7, 1989, J.Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterizationof Inorganic Compounds, W. L. Jolly (Prentice-Hall; 1970), pp. 461-3;Inorg. Chem., 18, 1497-1502 (1979); Inorg. Chem. 21, 2881-2885 (1982);Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960);and Journal of Physical Chemistry, 56, 22-25 (1952).

iii. Transition Metal Complexes of Macropolycyclic Rigid Ligands

Compositions herein may also suitably include as bleach catalyst atransition metal complex of a macropolycyclic rigid ligand. The phrase“macropolycyclic rigid ligand” is sometimes abbreviated as “MRL” indiscussion below. The amount used is a catalytically effective amount,suitably about 1 ppb or more, for example up to about 99.9%, moretypically about 0.001 ppm or more, preferably from about 0.05 ppm toabout 500 ppm (wherein “ppb” denotes parts per billion by weight and“ppm” denotes parts per million by weight).

Suitable transition metals e.g., Mn are illustrated hereinafter.“Macropolycyclic” means a MRL is both a macrocycle and is polycyclic.“Polycyclic” means at least bicyclic. The term “rigid” as used hereinherein includes “having a superstructure” and “cross-bridged”. “Rigid”has been defined as the constrained converse of flexibility: see D. H.Busch., Chemical Reviews., (1993), 93, 847-860, incorporated byreference. More particularly, “rigid” as used herein means that the MRLmust be determinably more rigid than a macrocycle (“parent macrocycle”)which is otherwise identical (having the same ring size and type andnumber of atoms in the main ring) but lacking a superstructure(especially linking moieties or, preferably cross-bridging moieties)found in the MRL's. In determining the comparative rigidity ofmacrocycles with and without superstructures, the practitioner will usethe free form (not the metal-bound form) of the macrocycles. Rigidity iswell-known to be useful in comparing macrocycles; suitable tools fordetermining, measuring or comparing rigidity include computationalmethods (see, for example, Zimmer, Chemical Reviews. (1995), 95(38),2629-2648 or Hancock et al., Inorganica Chimica Acta, (1989), 164,73-84.

Preferred MRL's herein are a special type of ultra-rigid ligand which iscross-bridged. A “cross-bridge” is nonlimitingly illustrated in 1.11hereinbelow. In 1.11, the cross-bridge is a —CH₂CH₂— moiety. It bridgesN¹ and N⁸ in the illustrative structure. By comparison, a “same-side”bridge, for example if one were to be introduced across N¹ and N¹² in1.11, would not be sufficient to constitute a “cross-bridge” andaccordingly would not be preferred.

Suitable metals in the rigid ligand complexes include Mn(II), Mn(III),Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I),Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V),Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI),Pd(II), Ru(II), Ru(III), and Ru(IV). Preferred transition-metals in theinstant transition-metal bleach catalyst include manganese, iron andchromium.

More generally, the MRL's (and the corresponding transition-metalcatalysts) herein suitably comprise:

(a) at least one macrocycle main ring comprising four or moreheteroatoms; and

(b) a covalently connected non-metal superstructure capable ofincreasing the rigidity of the macrocycle, preferably selected from

(i) a bridging superstructure, such as a linking moiety;

(ii) a cross-bridging superstructure, such as a cross-bridging linkingmoiety; and

(iii) combinations thereof.

The term “superstructure” is used herein as defined in the literature byBusch et al., see, for example, articles by Busch in “Chemical Reviews”.

Preferred superstructures herein not only enhance the rigidity of theparent macrocycle, but also favor folding of the macrocycle so that itcoordinates to a metal in a cleft. Suitable superstructures can beremarkably simple, for example a linking moiety such as any of thoseillustrated in FIG. 1 and FIG. 2 below, can be used.

wherein n is an integer, for example from 2 to 8, preferably less than6, typically 2 to 4, or

wherein m and n are integers from about 1 to 8, more preferably from 1to 3; Z is N or CH; and T is a compatible substituent, for example H,alkyl, trialkylammonium, halogen, nitro, sulfonate, or the like. Thearomatic ring in 1.10 can be replaced by a saturated ring, in which theatom in Z connecting into the ring can contain N, O, S or C.

Suitable MRL's are further nonlimitingly illustrated by the followingcompound:

This is a MRL in accordance with the invention which is a highlypreferred, cross-bridged, methyl-substituted (all nitrogen atomstertiary) derivative of cyclamn. Formally, this ligand is named5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadene using the extendedvon Baeyer system. See “A Guide to IUPAC Nomenclature of OrganicCompounds: Recommendations 1993”, R. Panico, W. H. Powell and J-C Richer(Eds.), Blackwell Scientific Publications, Boston, 1993; see especiallysection R-2.4.2.1.

Transition-metal bleach catalysts of Macrocyclic Rigid Ligands which aresuitable for use in the invention compositions can in general includeknown compounds where they conform with the definition herein, as wellas, more preferably, any of a large number of novel compounds expresslydesigned for the present laundry or cleaning uses, and non-limitinglyillustrated by any of the following:

Dichloro5,12-dimethyl-1,5,8,12-tetaazabicyclo[6.6.2]hexadecaneManganese(II)

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Hexafluorophosphate

Aquo-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Diaquo-5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II) Tetrafluoroborate

Dichloro-5,12dimethyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(III) Hexafluorophosphate

Dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-octyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II)

Dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecaneManganese(II).

(f) Other Bleach Catalysts

The compositions herein may comprise one or more other bleach catalysts.Preferred bleach catalysts are zwitterionic bleach catalysts, which aredescribed in U.S. Pat. No. 5,576,282 (especially3-(3,4dihydroisoquinolinium)propane sulfonate. Other bleach catalystsinclude cationic bleach catalysts are described in U.S. Pat. Nos.5,360,569, 5,442,066, 5,478,357, 5,370,826, 5,482,515, 5,550,256, and WO95/13351, WO 95/13352, and WO 95/13353.

As a practical matter, and not by way of limitation, the compositionsand cleaning processes herein can be adjusted to provide on the order ofat least one part per hundred million of the active bleach catalystspecies in the aqueous washing medium, and will preferably provide fromabout 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm toabout 10 ppm, and most preferably from about 0.1 ppm to about 5 ppm, ofthe bleach catalyst species in the wash liquor. In order to obtain suchlevels in the wash liquor of an automatic washing process, typicalcompositions herein will comprise from about 0.0005% to about 0.2%, morepreferably from about 0.004% to about 0.08%, of bleach catalyst,especially manganese or cobalt catalysts, by weight of the cleaningcompositions.

Preferably, the peroxygen source is selected from hydrogen peroxidesources selected from the group consisting of perborate compounds,percarbonate compounds, perphosphate compounds and mixtures thereof, anda bleach activator.

Preferably, the bleach activator is selected from the group consistingof hydrophobic bleach activators as disclosed herein.

The purpose of such a bleach system is to mitigate unwanteddecomposition of the organic catalyst, and to allow the peracid toachieve bleaching performance on a fabric in need of cleaning, such as astained fabric, in a wash solution prior to the availability of theorganic catalyst.

The period of time between the peracid becoming active in a washsolution and the organic catalyst compounds becoming active can be inthe range of from about 1 second to about 24 hours. Alternatively, sincethe organic catalyst compounds are relatively stable in the washsolution, the peracid can become active in the wash solution after theorganic catalyst compound becomes active or available.

The purpose of a delayed addition bleach system (which may or may not beused in conjunction with this invention) is to allow the peracid toachieve maximum bleaching performance on a fabric in need of cleaning,such as a stained fabric, in a wash solution prior to the introductionof the organic catalyst compound. In other words, a bleach systemcomprising a organic catalyst compound which becomes active in a washsolution after a fabric in need of cleaning has been added to the washsolution. Alternatively, since the organic catalyst compounds can haveincreased stability, a bleach system comprising an organic catalystcompound which becomes active in a wash solution prior to a fabric inneed of cleaning has been added to the wash solution may be used.

A preferred bleach system in accordance with the present invention is ableach system comprising:

(a) a peroxygen source; and

(b) a zwitterionic organic catalyst compound;

wherein the zwitterionic organic catalyst compound becomes active in awash solution containing said bleach system a period of time after saidperoxygen source becomes active. The peroxygen source, like discussedabove, is preferably selected from the group consisting of:

(i) preformed peracid compounds selected from the group consisting ofpercarboxylic acids and salts, percarbonic acids and salts, perimidicacids and salts, peroxymonosulfuric acids and salts, and mixturesthereof, and

(ii) hydrogen peroxide sources selected from the group consisting ofperborate compounds, percarbonate compounds, perphosphate compounds andmixtures thereof, and a bleach activator.

The bleach systems of the present invention also preferably comprise, inaddition to one or more organic catalysts, described hereinbefore, oneor more cleaning adjunct materials, preferably compatible with theorganic catalyst(s) and/or any enzymes present in the bleach system. Theterm “compatible”, as used herein, means the bleach system materials donot reduce the bleaching activity of the organic catalyst and/or anyenzymatic activity of any enzyme present in the bleach system to such anextent that the organic catalyst and/or enzyme is not effective asdesired during normal use situations. The term “cleaning adjunctmaterials”, as used herein, means any liquid, solid or gaseous materialselected for the particular type of bleach system desired and the formof the product (e.g., liquid; granule; powder, bar, paste; spray;tablet; gel; foam composition), which materials are also preferablycompatible with the protease enzyme(s) and bleaching agent(s) used inthe composition. Granular compositions can also be in “compact” form andthe liquid compositions can also be in a “concentrated” form.

The specific selection of cleaning adjunct materials are readily made byconsidering the surface, item or fabric to be cleaned, and the desiredform of the composition for the cleaning conditions during use (e.g.,through the wash detergent use). Examples of suitable cleaning adjunctmaterials include, but are not limited to, surfactants, builders,bleaches, bleach activators, bleach catalysts, other enzymes, enzymestabilizing systems, chelants, optical brighteners, soil releasepolymers, dye transfer agents, dispersants, suds suppressors, dyes,perfumes, colorants, filler salts, hydrotropes, photoactivators,fluorescers, fabric conditioners, hydrolyzable surfactants,preservatives, anti-oxidants, anti-shrinkage agents, anti-wrinkleagents, germicides, fungicides, color speckles, silvercare, anti-tarnishand/or anti-corrosion agents, alkalinity sources, solubilizing agents,carriers, processing aids, pigments and pH control agents as describedin U.S. Pat. Nos. 5,705,464, 5,710,115, 5,698,504, 5,695,679, 5,686,014and 5,646,101. Specific bleach system materials are exemplified indetail hereinafter.

If the cleaning adjunct materials are not compatible with the proteasevariant(s) in the bleach systems, then suitable methods of keeping thecleaning adjunct materials and the protease variant(s) separate (not incontact with each other) until combination of the two components isappropriate can be used. Suitable methods can be any method known in theart, such as gelcaps, encapulation, tablets, physical separation, etc.

Such bleach systems include detergent compositions for cleaning hardsurfaces, unlimited in form (e.g., liquid, granular, paste, foam, spray,etc.); detergent compositions for cleaning fabrics, unlimited in form(e.g., granular, liquid, bar formulations, etc.); dishwashingcompositions (unlimited in form and including both granular and liquidautomatic dishwashing); oral bleach systems, unlimited in form (e.g.,dentifrice, toothpaste and mouthwash formulations); and denture bleachsystems, unlimited in form (e.g., liquid, tablet).

The fabric bleach systems of the present invention are mainly intendedto be used in the wash cycle of a washing machine; however, other usescan be contemplated, such as pretreatment product for heavily-soiledfabrics, or soaking product; the use is not necessarily limited to thewashing-machine context, and the compositions of the present inventioncan be used alone or in combination with compatible handwashcompositions.

The bleach systems may include from about 1% to about 99.9% by weight ofthe composition of the cleaning adjunct materials.

As used herein, “non-fabric bleach systems” include hard surface bleachsystems, dishwashing compositions, oral bleach systems, denture bleachsystems and personal cleansing compositions.

When the bleach systems of the present invention are formulated ascompositions suitable for use in a laundry machine washing method, thecompositions of the present invention preferably contain both asurfactant and a builder compound and additionally one or more cleaningadjunct materials preferably selected from organic polymeric compounds,bleaching agents, additional enzymes, suds suppressors, dispersants,lime-soap dispersants, soil suspension and anti-redeposition agents andcorrosion inhibitors. Laundry compositions can also contain softeningagents, as additional cleaning adjunct materials.

The compositions of the present invention can also be used as detergentadditive products in solid or liquid form. Such additive products areintended to supplement or boost the performance of conventionaldetergent compositions and can be added at any stage of the cleaningprocess.

When formulated as compositions for use in manual dishwashing methodsthe compositions of the invention preferably contain a surfactant andpreferably other cleaning adjunct materials selected from organicpolymeric compounds, suds enhancing agents, group II metal ions,solvents, hydrotropes and additional enzymes.

If needed the density of the laundry detergent compositions hereinranges from 400 to 1200 g/litter, preferably 500 to 950 g/litter ofcomposition measured at 20° C.

The “compact” form of the bleach systems herein is best reflected bydensity and, in terms of composition, by the amount of inorganic fillersalt; inorganic filler salts are conventional ingredients of detergentcompositions in powder form; in conventional detergent compositions, thefiller salts are present in substantial amounts, typically 17-35% byweight of the total composition. In the compact compositions, the fillersalt is present in amounts not exceeding 15% of the total composition,preferably not exceeding 10%, most preferably not exceeding 5% by weightof the composition. The inorganic filler salts, such as meant in thepresent compositions are selected from the alkali andalkaline-earth-metal salts of sulfates and chlorides. A preferred fillersalt is sodium sulfate.

Liquid bleach systems according to the present invention can also be ina “concentrated form”, in such case, the liquid bleach systems accordingthe present invention will contain a lower amount of water, compared toconventional liquid detergents. Typically the water content of theconcentrated liquid bleach system is preferably less than 40%, morepreferably less than 30%, most preferably less than 20% by weight of thebleach system.

Cleaning Adjunct Materials

While not essential for the purposes of the present invention, severalconventional adjuncts illustrated hereinafter are suitable for use inthe instant bleach systems and may be desirably incorporated inpreferred embodiments of the invention, for example to assist or enhancecleaning performance, for treatment of the substrate to be cleaned, orto modify the aesthetics of the bleach systemn as is the case withperfumes, colorants, dyes or the like. The precise nature of theseadditional components, and levels of incorporation thereof, will dependon the physical form of the composition and the nature of the cleaningoperation for which it is to be used. Unless otherwise indicated, thebleach systems of the invention may for example, be formulated asgranular or powder-form all-purpose or “heavy-duty” washing agents,especially laundry detergents; liquid, gel or paste-form all-purposewashing agents, especially the so-called heavy-duty liquid types; liquidfine-fabric detergents; hand dishwashing agents or light dutydishwashing agents, especially those of the high-foaming type; machinedishwashing agents, including the various tablet, granular, liquid andrinse-aid types for household and institutional use; liquid cleaning anddisinfecting agents, including antibacterial hand-wash types, laundrybars, mouthwashes, denture cleaners, car or carpet shampoos, bathroomcleaners; hair shampoos and hair-rinses; shower gels and foam baths andmetal cleaners; as well as cleaning auxiliaries such as bleach additivesand “stain-stick” or pre-treat types.

Surfactants

The compositions of the present invention preferably contain a detersivesurfactant. The detersive surfactant is typically selected from thegroup consisting of anionic, nonionics, cationics, ampholytics,zwitterionics, and mixtures thereof. By selecting the type and amount ofdetersive surfactant, along with other adjunct ingredients disclosedherein, the present detergent compositions can be formulated to be usedin the context of laundry cleaning or in other different cleaningapplications, particularly including dishwashing. The particularsurfactants used can therefore vary widely depending upon the particularend-use envisioned. Suitable surfactants are described below. Examplesof suitable nonionic, anionic, cationic amphoteric and zwitterionicsurfactants are given in “Surface Active Agents and Detergents” (Vol. Iand II by Schwartz, Perry and Berch). A variety of such surfactants arealso generally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30,1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line23.

The surfactant is typically present at a level of from about 0.1%,preferably about 1%, more preferably about 5% by weight of the bleachsystems to about 99.9%, preferably about 80%, more preferably about 35%,most preferably 30% about by weight of the bleach systems.

Anionic Surfactants

Anionic surfactants useful in the present invention are preferablyselected from the group consisting of, linear alkylbenzene sulfonate,alpha olefin sulfonate, paraffin sulfonates, alkyl ester sulfonates,alkyl sulfates, alkyl alkoxy sulfate, alkyl sulfonates, alkyl alkoxycarboxylate, alkyl alkoxylated sulfates, sarcosinates, taurinates, andmixtures thereof. An effective amount, typically from about 0.5% toabout 90%, preferably about 5% to about 60%, more preferably from about10 to about 30%, by weight of anionic detersive surfactant can be usedin the present invention.

Alkyl sulfate surfactants are another type of anionic surfactant ofimportance for use herein. In addition to providing excellent overallcleaning ability when used in combination with polybydroxy fatty acidamides (see below), including good grease/oil cleaning over a wide rangeof temperatures, wash concentrations, and wash times, dissolution ofalkyl sulfates can be obtained, as well as improved formulability inliquid detergent formulations are water soluble salts or acids of theformula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferablyan alkyl or hydroxyalkyl having a C₁₀-C₂₀ alkyl component, morepreferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, and M is H or a cation,e.g., an alkali (Group IA) metal cation (e.g., sodium, potassium,lithium), substituted or unsubstituted ammonium cations such as methyl-,dimethyl-, and trimethyl ammonium and quaternary ammonium cations, e.g.,tetramethyl-ammonium and dimethyl piperdinium, and cations derived fromalkanolamines such as ethanolamine, diethanolamine, triethanolamine, andmixtures thereof, and the like. Typically, alkyl chains of C₁₂₋₁₆ arepreferred for lower wash temperatures (e.g., below about 50° C.) andC₁₆₋₁₈ alkyl chains are preferred for higher wash temperatures (e.g.,above about 50° C.).

Alkyl alkoxylated sulfate surfactants are another category of usefulanionic surfactant. These surfactants are water soluble salts or acidstypically of the formula RO(A)_(m)SO₃M wherein R is an unsubstitutedC₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkyl component,preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₈alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater thanzero, typically between about 0.5 and about 6, more preferably betweenabout 0.5 and about 3, and M is H or a cation which can be, for example,a metal cation (e.g., sodium, potassium, lithium, etc.), ammonium orsubstituted-ammonium cation. Alkyl ethoxylated sulfates as well as alkylpropoxylated sulfates are contemplated herein. Specific examples ofsubstituted ammonium cations include methyl-, dimethyl-,trimethyl-ammonium and quaternary ammonium cations, such astetramethyl-ammonium, dimethyl piperidinium and cations derived fromalkanolamines, e.g. monoethanolamine, diethanolamine, andtriethanolamine, and mixtures thereof. Exemplary surfactants are C₁₂-C₁₈alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈ alkyl polyethoxylate (2.25)sulfate, C₁₂-C₁₈ alkyl polyethoxylate (3.0) sulfate, and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate wherein M is conveniently selected fromsodium and potassium. Surfactants for use herein can be made fromnatural or synthetic alcohol feedstocks. Chain lengths represent averagehydrocarbon distributions, including branching.

Additionally and preferably, the surfactant may be a midchain branchedalkyl sulfate, midchain branched alkyl alkoxylate, or midchain branchedalkyl alkoxylate sulfate. These surfactants are further described in No.60/061,971, Oct. 14, 1997, No. 60/061,975, Oct. 14, 1997, No.60/062,086, Oct. 14, 1997, No. 60/061,916, Oct. 14, 1997, No.60/061,970, Oct. 14, 1997, No. 60/062,407, Oct. 14, 1997,. Othersuitable mid-chain branched surfactants can be found in U.S. Patentapplications Serial Nos. 60/032,035, 60/031,845, 60/031,916, 60/031,917,60/031,761, 60/031,762 and 60/031,844. Mixtures of these branchedsurfactants with conventional linear surfactants are also suitable foruse in the present compositions.

Another preferred anionic surfactant are the so-called modified alkylbenzene sulfonate surfactants, or MLAS. Some suitable MLAS surfactants,methods of making them and exemplary compositions are further describedin copending U.S. Patent applications Serial Nos. 60/053,319,60/053,318, 60/053,321, 60/053,209, 60/053,328, 60/053,186, 60/055,437,60/105,017, and 60/104,962,

Examples of suitable anionic surfactants are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).

Nonionic Detergent Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S.Pat. No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, at column 13,line 14 through column 16, line 6, incorporated herein by reference.Exemplary, non-limiting classes of useful nonionic surfactants include:amine oxides, alkyl ethoxylate, alkanoyl glucose amide, alkyl betaines,sulfobetaine and mixtures thereof.

Amine oxides are semi-polar nonionic surfactants and includewater-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl groups and hydroxyalkyl groups containing from about1 to about 3 carbon atoms; water-soluble phosphine oxides containing onealkyl moiety of from about 10 to about 18 carbon atoms and 2 moietiesselected from the group consisting of alkyl groups and hydroxyalkylgroups containing from about 1 to about 3 carbon atoms; andwater-soluble sulfoxides containing one alkyl moiety of from about 10 toabout 18 carbon atoms and a moiety selected from the group consisting ofalkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxidesurfactants having the formula

wherein R³ is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixturesthereof containing from about 8 to about 22 carbon atoms; R⁴ is analkylene or hydroxyalkylene group containing from about 2 to about 3carbon atoms or mixtures thereof; x is from 0 to about 3; and each R⁵ isan alkyl or hydroxyalkyl group containing from about 1 to about 3 carbonatoms or a polyethylene oxide group containing from about 1 to about 3ethylene oxide groups. The R⁵ groups can be attached to each other,e.g., through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants in particular include C₁₀-C₁₈ alkyldimethyl amine oxides and C₈-C₁₂ alkoxy ethyl dihydroxy ethyl amineoxides. Preferably the amine oxide is present in the composition in aneffective amount. more preferably from about 0.1% to about 20%, evenmore preferably about 0.1% to about 15%, even more preferably still fromabout 0.5% to about 10%, by weight.

The polyethylene, polypropylene, and polybutylene oxide condensates ofalkyl phenols. In general, the polyethylene oxide condensates arepreferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 12 carbonatoms in either a straight chain or branched chain configuration withthe alkylene oxide. In a preferred embodiment, the ethylene oxide ispresent in an amount equal to from about 5 to about 25 moles of ethyleneoxide per mole of alkyl phenol. Commercially available nonionicsurfactants of this type include Igepal® CO-630, marketed by the GAFCorporation; and Triton® X-45, X-114, X-100, and X-102, all marketed bythe Rohm & Haas Company. These compounds are commonly referred to asalkyl phenol alkoxylates, (e.g., alkyl phenol ethoxylates).

The condensation products of aliphatic alcohols with from about 1 toabout 25 moles of ethylene oxide. The alkyl chain of the aliphaticalcohol can either be straight or branched, primary or secondary, andgenerally contains from about 8 to about 22 carbon atoms. Particularlypreferred are the condensation products of alcohols having an alkylgroup containing from about 10 to about 20 carbon atoms with from about2 to about 18 moles of ethylene oxide per mole of alcohol. Examples ofcommercially available nonionic surfactants of this type includeTergitol® 15-S-9 (the condensation product of C₁₁-C₁₅ linear secondaryalcohol with 9 moles ethylene oxide), Tergitol® 24-L-6 NMW (thecondensation product of C₁₂-C₁₄ primary alcohol with 6 moles ethyleneoxide with a narrow molecular weight distribution), both marketed byUnion Carbide Corporation; Neodol® 45-9 (the condensation product ofC₁₄-C₁₅ linear alcohol with 9 moles of ethylene oxide), Neodol® 23-6.5(the condensation product of C₁₂-C₁₃ linear alcohol with 6.5 moles ofethylene oxide), Neodol® 45-7 (the condensation product of C₁₄-C₁₅linear alcohol with 7 moles of ethylene oxide), Neodol® 45-4 (thecondensation product of C₁₄-C₁₅ linear alcohol with 4 moles of ethyleneoxide), marketed by Shell Chemical Company, and Kyro® EOB (thecondensation product of C₁₃-C₁₅ alcohol with 9 moles ethylene oxide),marketed by The Procter & Gamble Company. Other commercially availablenonionic surfactants include Dobanol 91-8® marketed by Shell ChemicalCo. and Genapol UD080® marketed by Hoechst. This category of nonionicsurfactant is referred to generally as “alkyl ethoxylates.”

The preferred alkylpolyglycosides have the formula

R²O(C_(n)H_(2n)O)_(t)(glycosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkyl-phenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantly the 2-position.

Fatty acid amide surfactants having the formula:

wherein R⁶ is an alkyl group containing from about 7 to about 21(preferably from about 9 to about 17) carbon atoms and each R⁷ isselected from the group consisting of hydrogen, C₁-C₄ alkyl, C₁-C₄hydroxyalkyl, and —(C²H₄O)_(x)H where x varies from about 1 to about 3.

Preferred amides are C₈-C₂₀ ammonia amides, monoethanolamides,diethanolamides, and isopropanolamides.

Preferably the nonionic surfactant, when present in the composition, ispresent in an effective amount, more preferably from about 0.1% to about20%, even more preferably about 0.1% to about 15%, even more preferablystill from about 0.5% to about 10%, by weight.

Polyhydroxy Fatty Acid Amide Surfactant

The detergent compositions hereof may also contain an effective amountof polyhydroxy fatty acid amide surfactant. By “effective amount” ismeant that the formulator of the composition can select an amount ofpolyhydroxy fatty acid amide to be incorporated into the compositionsthat will improve the cleaning performance of the detergent composition.In general, for conventional levels, the incorporation of about 1%, byweight, polyhydroxy fatty acid amide will enhance cleaning performance.

The detergent compositions herein will typically comprise about 1%weight basis, polyhydroxy fatty acid amide surfactant, preferably fromabout 3% to about 30%, of the polyhydroxy fatty acid amide. Thepolyhydroxy fatty acid amide surfactant component comprises compounds ofthe structural formula:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl,or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, morepreferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁-C₁₅ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z will be a glycityl. Suitable reducing sugars includeglucose, fructose, maltose, lactose, galactose, mannose, and xylose. Asraw materials, high dextrose corn syrup, high fructose corn syrup, andhigh maltose corn syrup can be utilized as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n−1)—CH₂OH, —CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, andalkoxylated derivatives thereof, where n is an integer from 3 to 5,inclusive, and R′ is H or a cyclic or aliphatic monosaccharide. Mostpreferred are glycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

R′ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.

R²—CO—N< can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art.In general, they can be made by reacting an alkyl amine with a reducingsugar in a reductive amination reaction to form a corresponding N-alkylpolyhydroxyamine, and then reacting the N-alkyl polyhydroxyamine with afatty aliphatic ester or triglyceride in a condensation/amidation stepto form the N-alkyl, N-polyhydroxy fatty acid amide product. Processesfor making compositions containing polyhydroxy fatty acid amides aredisclosed, for example, in G.B. Patent Specification 809,060, publishedFeb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No. 2,965,576,issued Dec. 20, 1960 to E. R. Wilson, and U.S. Pat. No. 2,703,798,Anthony M. Schwartz, issued Mar. 8, 1955, and U.S. Pat. No. 1,985,424,issued Dec. 25, 1934 to Piggott, each of which is incorporated herein byreference.

Diamines

The preferred liquid detergent compositions, such as light duty liquid,LDL compositions, useful in the methods of the present invention mayfurther comprise one or more diamines, preferably an amount of diaminesuch that the ratio of anionic surfactant present to the diamine is fromabout 40:1 to about 2:1. Said diamines provide for increased removal ofgrease and greasy food material while maintaining suitable levels ofsuds.

The diamines suitable for use in the compositions of the presentinvention have the formula:

wherein each R²⁰ is independently selected from the group consisting ofhydrogen, C₁-C₄ linear or branched alkyl, alkyleneoxy having theformula:

—(R²¹O)_(y)R²²

wherein R²¹ is C₂-C₄ linear or branched alkylene, and mixtures thereof,R²² is hydrogen, C₁-C₄ alkyl, and mixtures thereof; y is from 1 to about10; X is a unit selected from:

i) C₃-C₁₀ linear alkylene, C₃-C₁₀ branched alkylene, C₃-C₁₀ cyclicalkylene, C₃-C₁₀ branched cyclic alkylene, an alkyleneoxyalkylene havingthe formula:

—(R²¹O)_(y)R²¹—

 wherein R²¹ and y are the same as defined herein above;

ii) C₃-C₁₀ linear, C₃-C₁₀ branched linear, C₃-C₁₀ cyclic, C₃-C₁₀branched cyclic alkylene, C₆-C₁₀ arylene, wherein said unit comprisesone or more electron donating or electron withdrawing moieties whichprovide said diamine with a pK_(a) greater than about 8; and

iii) mixtures of (i) and (ii)

provided said diamine has a pK_(a) of at least about 8.

The preferred diamines of the present invention have a pK₁ and pK₂ whichare each in the range of from about 8 to about 11.5, preferably in therange of from about 8.4 to about 11, more preferably from about 8.6 toabout 10.75. For the purposes of the present invention the term “pK_(a)”stands equally well for the terms “pK₁” and “pK₂” either separately orcollectively. The term pK_(a) as used herein throughout the presentspecification in the same manner as used by those of ordinary skill inthe art. pK_(a) values arc readily obtained from standard literaturesources, for example, “Critical Stability Constants: Volume 2, Amines”by Smith and Martel, Plenum Press, N.Y. and London, (1975).

As an applied definition herein, the pK_(a) values of the diamincs arespecified as being measured in an aqueous solution at 25° C. having anionic strength of from about 0.1 to about 0.5 M. As used herein, thepK_(a) is an equilibrium constant dependent upon temperature and ionicstrength, therefore, value reported by literature references, notmeasured in the above described manner, may not be within full agreementwith the values and ranges which comprise the present invention. Toeliminate ambiguity, the relevant conditions and/or references used forpK_(a)'s of this invention are as defined herein or in “CriticalStability Constants: Volume 2, Amines”. One typical method ofmeasurement is the potentiometric titration of the acid with sodiumhydroxide and determination of the pK_(a) by suitable methods asdescribed and referenced in “The Chemist's Ready Reference Handbook” byShugar and Dean, McGraw Hill, NY, 1990.

Preferred diamines for performance and supply considerations are1,3-bis(methylamino)cyclohexane, 1,3-diaminopropane (pK₁=10.5; pK₂=8.8),1,6-diaminohexane (pK₁=11; pK₂=10), 1,3-diaminopentane (Dytek EP)(pK₁=10.5; pK₂=8.9), 2-methyl 1,5-diaminopentane (Dytek A) (pK₁=11.2;pK₂=10.0). Other preferred materials are the primary/primary diamineshaving alkylene spacers ranging from C₄-C₈. In general, primary diaminesare preferred over secondary and tertiary diamines.

The following are non-limiting examples of diamines suitable for use inthe present invention.

1-N,N-dimethylamnino-3-aminopropane having the formula:

1,6-diaminohexane having the formula:

1,3-diaminopropane having the formula:

2-methyl-1,5-diaminopentane having the formula:

1,3-diamninopentane, available under the tradename Dytek EP, having theformula:

1,3-diaminobutane having the formula:

Jeffamine EDR 148, a diamine having an alkyleneoxy backbone, having theformula:

3-methyl-3-aminoethyl-5-dimethyl-1-aminocyclohexane (isophorone diamine)having the formula:

 and

1,3-bis(methylamino)cyclohexane having the formula:

Additional Detergent Components

The following are non-limiting examples of additional detergentcomponents (adjunct ingredients) useful in the bleach systems,especially laundry detergent compositions, of the present invention,said adjunct ingredients include builders, optical brighteners, soilrelease polymers, dye transfer agents, dispersants, enzymes, sudssuppressers, dyes, perfumes, colorants, filler salts, hydrotropes,photoactivators, fluorescers, fabric conditioners, hydrolyzablesurfactants, preservatives, anti-oxidants, chelants, stabilizers,anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anticorrosion agents, and mixtures thereof.

Builders

The bleach systems of the present invention preferably comprise one ormore detergent builders or builder systems. When present, thecompositions will typically comprise at least about 1% builder,preferably from about 5%, more preferably from about 10% to about 80%,preferably to about 50%, more preferably to about 30% by weight, ofdetergent builder.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder.Formulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂:Na₂O ratio in the range 1.6:1 to 3.2:1and layered silicates, such as the layered sodium silicates described inU.S. Pat. No. 4,664,839 Rieck, issued May 12, 1987. NaSKS-6 is thetrademark for a crystalline layered silicate marketed by Hoechst(commonly abbreviated herein as “SKS-6”). Unlike zeolite builders, theNa SKS-6 silicate builder does not contain aluminum. NaSKS-6 has thedelta-Na₂SiO₅ morphology form of layered silicate. It can be prepared bymethods such as those described in German DE-A-3,417,649 andDE-A-3,742,043. SKS-6 is a highly preferred layered silicate for useherein, but other such layered silicates, such as those having thegeneral formula NaMSi_(x)O_(2x+1).yH₂O wherein M is sodium or hydrogen,x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to20, preferably 0 can be used herein. Various other layered silicatesfrom Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, betaand gamma forms. As noted above, the delta-Na₂SiO₅ (NaSKS-6 form) ismost preferred for use herein. Other silicates may also be useful suchas for example magnesium silicate, which can serve as a crispening agentin granular formulations, as a stabilizing agent for oxygen bleaches,and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

[M_(z)(zAlO₂)_(y) ].xH₂O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-cccurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂ ].xH2O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the alumindsilicate has a article size of about0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “poly-carboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in U.S. Pat. No. 3,128,287 Berg, issued Apr. 7, 1964, U.S.Pat. No. 3,635,830 Lamberti et al., issued Jan. 18, 1972, and U.S. Pat.No. 3,936,448 Lamberti, issued Feb. 3, 1976. See also “TMS/TDS” buildersof U.S. Pat. No. 4,663,071 Bush et al., issued May 5, 1987. Suitableether polycarboxylates also include cyclic compounds, particularlyalicyclic compounds, such as those described in U.S. Pat. No. 3,923,679Rapko, issued Dec. 2, 1975; U.S. Pat. No. 4,158,635 Crutchfield et al.,issued Jun. 19, 1979; U.S. Pat. No. 4,120,874 Crutchfield et al., issuedOct. 17, 1978; and U.S. Pat. No. 4,102,903 Crutchfield et al., issuedJul. 25, 1978.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymer of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the bleach systems of the present invention are the3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅-C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al., issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂-C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Chelating Agents

The bleach systems herein may also optionally contain one or more ironand/or manganese chelating agents. Such chelating agents can be selectedfrom the group consisting of amino carboxylates, amino phosphonates,polyfunctionally-substituted aromatic chelating agents and mixturestherein, all as hereinafter defined. Without intending to be bound bytheory, it is believed that the benefit of these materials is due inpart to their exceptional ability to remove iron and manganese ions fromwashing solutions by formation of soluble chelates.

Examples of suitable chelating agents and levels of use are described inU.S. Pat. Nos. 5,576,282 and 5,728,671.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate (“EDDS”), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

The compositions herein may also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% by weight of the bleach systems herein to about 15%, morepreferably 3.0% by weight of the bleach systems herein.

Dye Transfer Inhibiting Agents

The bleach systems of the present invention may also include one or morecompounds, dye transfer inhibiting agents, for inhibiting dye transferfrom one fabric to another of solubilized and suspended dyes encounteredduring fabric laundering and conditioning operations involving coloredfabrics.

Suitable polymeric dye transfer inhibiting agents include, but are notlimited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers,copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.Examples of such dye transfer inhibiting agents are disclosed in U.S.Pat. Nos. 5,707,950 and 5,707,951.

Additional suitable dye transfer inhibiting agents include, but are notlimited to, cross-linked polymers. Cross-linked polymers are polymerswhose backbone are interconnected to a certain degree; these links canbe of chemical or physical nature, possibly with active groups on thebackbone or on branches. Cross-linked polymers have been described inthe Journal of Polymer Science, volume 22, pages 1035-1039.

In one embodiment, the cross-linked polymers are made in such a way thatthey form a three-dimensional rigid structure, which can entrap dyes inthe pores formed by the three-dimensional structure.

In another embodiment, the cross-linked polymers entrap dyes byswelling.

Suitable cross-linked polymers are described in the co-pending Europeanpatent application 94870213.9.

Addition of such polymers also enhances the performance of the enzymeswithin the bleach systems herein.

The dye transfer inhibiting agents have the ability to complex or adsorbfugitive dyes wash out of dyed fabrics before the dyes have theopportunity to become attached to other articles in the wash.

When present in the bleach systems herein, the dye transfer inhibitingagents are present at levels from about 0.0001%, more preferably about0.01%, most preferably about 0.05% by weight of the bleach systems toabout 10%, more preferably about 2%, most preferably about 1% by weightof the bleach systems.

Dispersants

The bleach systems of the present invention can also containdispersants. Suitable water-soluble organic salts are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other bynot more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000-5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 1,000 to100,000.

Especially, copolymer of acrylate and methylacrylate such as the 480Nhaving a molecular weight of 4000, at a level from 0.5-20% by weight ofcomposition can be added in the detergent compositions of the presentinvention.

The compositions of the invention may contain a lime soap peptisercompound, which has a lime soap dispersing power (LSDP), as definedhereinafter of no more than 8, preferably no more than 7, mostpreferably no more than 6. The lime soap peptiser compound is preferablypresent at a level from 0% to 20% by weight.

A numerical measure of the effectiveness of a lime soap peptiser isgiven by the lime soap dispersant power (LSDP) which is determined usingthe lime soap dispersant test as described in an article by H. C.Borghetty and C. A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages88-90, (1950). This lime soap dispersion test method is widely used bypractitioners in this art field being referred to, for example, in thefollowing review articles; W. N. Linfield, Surfactant science Series,Volume 7, page 3; W. N. Linfield, Tenside surf. det., volume 27, pages159-163, (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics andToiletries, volume 104, pages 71-73, (1989). The LSDP is the % weightratio of dispersing agent to sodium oleate required to disperse the limesoap deposits formed by 0.025 g of sodium oleate in 30 ml of water of333 ppm CaCo₃ (Ca:Mg=3:2) equivalent hardness.

Surfactants having good lime soap peptiser capability will includecertain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates andethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accordwith the present invention include C₁₆-C₁₈ dimethyl amine oxide, C₁₂-C₁₈alkyl ethoxysulfates with an average degree of ethoxylation of from 1-5,particularly C₁₂-C₁₅ alkyl ethoxysulfate surfactant with a degree ofethoxylation of amount 3 (LSDP=4), and the C₁₄-C₁₅ ethoxylated alcoholswith an average degree of ethoxylation of either 12 (LSDP=6) or 30, soldunder the tradenames Lutensol A012 and Lutensol A030 respectively, byBASF GmbH.

Polymeric lime soap peptisers suitable for use herein are described inthe article by M. K. Nagarajan, W. F. Masler, to be found in Cosmeticsand Toiletries, volume 104, pages 71-73, (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminobexanoyl]benzenesulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate,4-[N-decanoylaminohexanoyl]benzene sulfonate and mixtures thereof; andnonanoyloxy benzene sulfonate together with hydrophilic/hydrophobicbleach formulations can also be used as lime soap peptisers compounds.

Enzymes

The bleach systems can comprise in addition to the amylase of thepresent invention one or more detergent enzymes which provide cleaningperformance and/or fabric care benefits. Such enzymes can includeproteases, amylases, cellutases and lipases. They may be incorporatedinto the non-aqueous liquid bleach systems herein in the form ofsuspensions, “marumes” or “prills”. Another suitable type of enzymecomprises those in the form of slurries of enzymes in nonionicsurfactants, e.g., the enzymes marketed by Novo Nordisk under thetradename “SL” or the microencapsulated enzymes marketed by Novo Nordiskunder the tradename “LDP.” Suitable enzymes and levels of use aredescribed in U.S. Pat. No. 5,576,282.

Enzymes added to the compositions herein in the form of conventionalenzyme prills are especially preferred for use herein. Such prills willgenerally range in size from about 100 to 1,000 microns, more preferablyfrom about 200 to 800 microns and will be suspended throughout thenon-aqueous liquid phase of the composition. Prills in the compositionsof the present invention have been found, in comparison with otherenzyme forms, to exhibit especially desirable enzyme stability in termsof retention of enzymatic activity over time. Thus, compositions whichutilize enzyme prills need not contain conventional enzyme stabilizingsuch as must frequently be used when enzymes are incorporated intoaqueous liquid detergents.

Examples of suitable enzymes include, but are not limited to,hennicellulases, peroxidases, proteases, cellulases, xylanases, lipases,phospholipases, esterases, cutinases, pectinases, keratanases,reductases, oxidases, phenoloxidases, lipoxygenases, ligninases,pullulanases, tannases, pentosanases, malanases, β-glucanases,arabinosidases, hyaluronidase, chondroitinase, laccase, known amylases,mannanases, xyloglucanases and mixtures thereof. A preferred combinationis a bleach system having a cocktail of conventional applicable enzymeslike protease, lipase, cutinase and/or cellulase in conjunction with theamylase of the present invention.

Examples of such suitable enzymes are disclosed in U.S. Pat. Nos.5,576,282, 5,728,671 and 5,707,950

Suitable proteases are the subtilisins which are obtained fromparticular strains of B. subtilis and B. licheniformis (subtilisin BPNand BPN). One suitable protease is obtained from a strain of Bacillus,having maximum activity throughout the pH range of 8-12, developed andsold as ESPERASE® by Novo Industries A/S of Denmark, hereinafter “Novo”.The preparation of this enzyme and analogous enzymes is described in GB1,243,784 to Novo. Other suitable proteases include ALCALASE®, DURAZYM®and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM®(protein engineered Maxacal) from Gist-Brocades. Proteolytic enzymesalso encompass modified bacterial serine proteases, such as thosedescribed in European Patent Application Serial Number 87 303761.8,filed Apr. 28, 1987 (particularly pages 17, 24 and 98), and which iscalled herein “Protease B”, and in European Patent Application 199,404,Venegas, published Oct. 29, 1986, which refers to a modified bacterialserine protealytic enzyme which is called “Protease A” herein. Morepreferred is what is called herein “Protease C”, which is a variant ofan alkaline serine protease from Bacillus in which lysine replacedarginine at position 27, tyrosine replaced valine at position 104,serine replaced asparagine at position 123, and alanine replacedthreonine at position 274. Protease C is described in EP 90915958:4,corresponding to WO 91/06637, Published May 16, 1991. Geneticallymodified variants, particularly of Protease C, are also included herein.See also a high pH protease from Bacillus sp. NCIMB 40338 described inWO 93/18140 A to Novo. Enzymatic detergents comprising protease, one ormore other enzymes, and a reversible protease inhibitor are described inWO 92/03529 A to Novo. When desired, a protease having decreasedadsorption and increased hydrolysis is available as described in WO95/07791 to Procter & Gamble. A recombinant trypsin-like protease fordetergents suitable herein is described in WO 94/25583 to Novo.

In more detail, the protease referred to as “Protease D” is a carbonylhydrolase variant having an amino acid sequence not found in nature,which is derived from a precursor carbonyl hydrolase by substituting adifferent amino acid for a plurality of amino acid residues at aposition in said carbonyl hydrolase equivalent to position +76,preferably also in combination with one or more amino acid residuepositions equivalent to those selected from the group consisting of +99,+101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,and/or +274 according to the numbering of Bacillus amyloliquefacienssubtilisin, as described in WO 95/10615 published Apr. 20, 1995 byGenencor International. Also suitable for the present invention areproteases described in patent applications EP 251 446 and WO91/06637 andprotease BLAP® described in WO91/02792. The proteolytic enzymes areincorporated in the bleach systems of the present invention a level offrom 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from0.005% to 0.1% pure enzyme by weight of the composition.

Useful proteases are also described in PCT publications: WO 95/30010published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/30011published Nov. 9, 1995 by The Procter & Gamble Company; WO 95/29979published Nov. 9, 1995 by The Procter & Gamble Company.

Other particularly useful proteases are multiply-substituted proteasevariants comprising a substitution of an amino acid residue with anothernaturally occurring amino acid residue at an amino acid residue positioncorresponding to position 103 of Bacillus amyloliquefaciens subtilisinin combination with a substitution of an amino acid residue with anothernaturally occurring amino acid residue at one or more amino acid residuepositions corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17,18, 19, 20, 21, 22, 24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62,68, 72, 75, 76, 77, 78, 79, 86, 87, 89, 97, 98, 99, 101, 102, 104, 106,107, 109, 111, 114, 116, 117, 119, 121, 123, 126, 128, 130, 131, 133,134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167, 170, 173,174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205,206, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227,228, 230, 232, 236, 237, 238, 240, 242, 243, 244, 245, 246, 247, 248,249, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263,265, 268, 269, 270, 271, 272, 274 and 275 of Bacillus amyloliquefacienssubtilisin; wherein when said protease variant includes a substitutionof amino acid residues at positions corresponding to positions 103 and76, there is also a substitution of an amino acid residue at one or moreamino acid residue positions other than amino acid residue positionscorresponding to positions 27, 99, 101, 104, 107, 109, 123, 128, 166,204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of Bacillusamylolquefaciens subtilisin and/or multiply-substituted proteasevariants comprising a substitution of an amino acid residue with anothernaturally occurring amino acid residue at one or more amino acid residuepositions corresponding to positions 62, 212, 230, 232, 252 and 257 ofBacillus amyloliquefaiens subtilisin as described in PCT PublishedApplication Nos. WO 99/20727, WO 99/20726, and WO 99/20723 all owned byThe Procter & Gamble Company.

More preferably the protease variant includes a substitution setselected from the group consisting of:

12/76/103/104/130/222/245/261;

62/103/104/159/232/236/245/248/252;

62/103/104/159/213/232/236/245/248/252;

62/101/103/104/159/212/213/232/236/245/248/252;

68/103/104/159/232/236/245;

68/103/104/159/230/232/236/245;

68/103/104/159/209/232/236/245;

68/103/104/159/232/236/245/257;

68/76/103/104/159/213/232/236/245/260;

68/103/104/159/213/232/236/245/248/252;

68/103/104/159/183/232/236/245/248/252;

68/103/104/159/185/232/236/245/248/252;

68/103/104/159/185/210/232/236/245/248/252;

68/103/104/159/210/232/236/245/248/252;

68/103/104/159/213/232/236/245;

98/103/104/159/232/236/245/248/252;

98/102/103/104/159/212/232/236/245/248/252;

 101/103/104/159/232/236/245/248/252;

102/103/104/159/232/236/245/248/252;

103/104/159/230/236/245;

103/104/159/232/236/245/248/252;

103/104/159/217/232/236/245/248/252;

103/104/130/159/232/236/245/248/252;

103/104/131/159/232/236/245/248/252;

103/104/159/213/232/236/245/248/252;

and

103/104/159/232/236/245.

Still even more preferably the protease variant includes a substitutionset selected from the group consisting of:

12R/76D/103A/104T/130T/222S/245R/261D;

62D/103A/104I/159D/232V/236H/245R/248D/252K;

62D/103A/104I/159D/213R/232V/236H/245R/248D/252K;

68A/103A/104I/159D/209W/232V/236H/245R;

68A/76D/103A/104I/159D/213R/232V/236H/245R/260A;

68A/103A/104I/159D/213E/232V/236H/245R/248D/252K;

68A/103A104I/159D/183D/232V/236H/245R/248D/252K;

68A/103A/104I/159D/232V/236H/245R;

68A/103A/104I/159D/230V/232V/236H/245R;

68A/103A/104I/159D/232V/236H/245R/257V;

68A/103A/104I/159D/213G/232V/236H/245R/248D/252K;

68A/103A/104I/159D/185D/232V/236H/245R/248D/252K;

68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K;

68A/103A/104I/159D/210L/232V/236H/245R/248D/252K;

68A/103A/104I/159D/213G/232V/236H/245R;

98L/103A/104I/159D/232V/236H/245R/248D/252K;

98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K;

101G/103A/104I/159D/232V/236H/245R/248D/252K;

102A/103A/104I/159D/232V/236H/245R/243D/252K;

103A/104I/159D/230V/236H/245R;

103A/104I/159D/232V/236H/245R/248D/252K;

103A/104I/159D/217E/232V/236H/245R/248D/252K;

 103A/104I/130G/159D/232V/236H/245R/248D/252K;

103A/104I/131V/159D/232V/236H/245R/248D/252K;

103A/104I/159D/213R/232V/236H/245R/248D/252K;

and

103A/104I/159D/232V/236H/245R.

Most preferably the protease variant includes the substitution set101/103/104/159/232/236/245/248/252, preferably101G/103A/104I/159D/232V/236H/245R/248D/252K.

The cellulases usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, which discloses fungal cellulase produced fromHumicola insolens. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800.

Other suitable cellulases are cellulases originated from Humicolainsolens having a molecular weight of about 50 KDa, an isoelectric pointof 5.5 and containing 415 amino acids; and a ⁻43 kD endoglucanasederived from Humicola insolens, DSM 1800, exhibiting cellulase activity;a preferred endoglucanase component has the amino acid sequencedisclosed in PCT Patent Application No. WO 91/17243. Also suitablecellulases are the EGIII cellulases from Trichoderma longibrachiatumdescribed in WO94/21801, Genencor, published Sep. 29, 1994. Especiallysuitable cellulases are the cellulases having color care benefits.Examples of such cellulases are cellulases described in European patentapplication No. 91202879.2, filed Nov. 6, 1991 (Novo). Carezyme andCelluzyme (Novo Nordisk A/S) are especially useful. See also WO91/17243.

Peroxidase enzymes are known in the art, and include, for example,horseradish peroxidase, ligninase and haloperoxidase such as chloro- andbromo-peroxidase. Peroxidase-containing bleach systems are disclosed,for example, in U.S. Pat. Nos. 5,576,282, 5,728,671 and 5,707,950, PCTInternational Applications WO 89/099813, WO89/09813 and in EuropeanPatent application EP No. 91202882.6, filed on Nov. 6, 1991 and EP No.96870013.8, filed Feb. 20, 1996. Also suitable is the laccase enzyme.

Preferred enhancers are substituted phenthiazine and phenoxasine10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylicacid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine(described in WO 94/12621) and substituted syringates (C3-C5 substitutedalkyl syringates) and phenols. Sodium percarbonate or perborate arepreferred sources of hydrogen peroxide.

Said peroxidases are normally incorporated in the bleach system atlevels from 0.0001% to 2% of active enzyme by weight of the bleachsystem.

Other preferred enzymes that can be included in the bleach systems ofthe present invention include lipases. Suitable lipase enzymes fordetergent usage include those produced by microorganisms of thePseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, asdisclosed in British Patent 1,372,034. Suitable lipases include thosewhich show a positive immunological cross-reaction with the antibody ofthe lipase, produced by the microorganism Pseudomonas fluorescent IAM1057. This lipase is available from Amano Pharmaceutical Co. Ltd.,Nagoya, Japan, under the trade name Lipase P “Amano,” hereinafterreferred to as “Amano-P”. Other suitable commercial lipases includeAmano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosumvar. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.Especially suitable lipases are lipases such as M1 LIPASE® and LIPOMAX®(Gist-Brocades) and LIPOLASE® and LIPOLASE ULTRA®(Novo) which have foundto be very effective when used in combination with the compositions ofthe present invention.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as aspecial kind of lipase, namely lipases which do not requite interfacialactivation. Addition of cutinases to bleach systems have been describedin e.g. WO 88/09367 (Genencor).

The lipases and/or cutinases are normally incorporated in the bleachsystem at levels from 0.0001% to 2% of active enzyme by weight of thebleach system.

Known amylases (α and/or β) can be included for removal ofcarbohydrate-based stains. WO 94/02597, Novo Nordisk A/S published Feb.03, 1994, describes cleaning compositions which incorporate mutantamylases. See also WO94/18314, Genencor, published Aug. 18, 1994 andWO95/10603, Novo Nordisk A/S, published Apr. 20, 1995. Other amylasesknown for use in bleach systems include both α- and β-amylases.α-Amylases are known in the art and include those disclosed in U.S. Pat.No. 5,003,257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123; EP525,610; EP 368,341; and British Patent Specification No. 1,296,839(Novo). Other suitable amylase are stability-enhanced amylases includingPURAFACT OX AM® described in WO 94/18314, published Aug. 18, 1994 andWO96/05295, Genencor, published Feb. 22, 1996 and amylase variants fromNovo Nordisk A/S, disclosed in WO 95/10603, published April 95.

Examples of commercial α-amylases products, are TERMAMYL®, BAN®,FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A/S Denmark.WO95/26397 describes other suitable amylases: α-amylases characterizedby having a specific activity at least 25% higher than the specificactivity of TERMAMYL® at a temperature range of 25° C. to 55° C. and ata pH value in the range of 8 to 10, measured by the Phadebas® α-amylaseactivity assay. Other amylolytic enzymes with improved properties withrespect to the activity level and the combination of thermostability anda higher activity level are described in WO95/35382.

The compositions of the present invention may also comprise a mannanaseenzyme. Preferably, the mannanase is selected from the group consistingof: three mannans-degrading enzymes: EC 3.2.1.25: β-mannosidase, EC3.2.1.78: Endo-1,4-β-mannosidase, referred therein after as “mannanase”and EC 3.2.1.100: 1,4-β-mannobiosidase and mixtures thereof. (IUPACClassification—Enzyme nomenclature, 1992 ISBN 0-12-227165-3 AcademicPress).

More preferably, the treating compositions of the present invention,when a mannanase is present, comprise a β-1,4-Mannosidase (E.C.3.2.1.78) referred to as Mannanase. The term “mannanase” or“galactomannanase” denotes a mannanase enzyme defined according to theart as officially being named mannan endo-1,4-beta-mannosidase andhaving the alternative names beta-mannanase and endo-1,4-mannanase andcatalysing the reaction: random hydrolysis of 1,4-beta-D-mannosidiclinkages in mannans, galactomannans, glucomannans, andgalactoglucomannans.

In particular, Mannanases (EC 3.2.1.78) constitute a group ofpolysaccharases which degrade mannans and denote enzymes which arecapable of cleaving polyose chains containing mannose units, i.e. arecapable of cleaving glycosidic bonds in mannans, glucomannans,galactomannans and galactogluco-mannans. Mannans are polysaccharideshaving a backbone composed of β-1,4-linked mannose; glucomannans arepolysaccharides having a backbone or more or less regularly alternatingβ-1,4 linked mannose and glucose; galactomannans and galactoglucomannansare mannans and glucomannans with α-1,6 linked galactose sidebranches.These compounds may be acetylated.

The degradation of galactomannans and galactoglucomannans is facilitatedby full or partial removal of the galactose sidebranches. Further thedegradation of the acetylated mannans, glucomannans, galactomannans andgalactoglucomannans is facilitated by full or partial deacetylation.Acetyl groups can be removed by alkali or by mannan acetylesterases. Theoligomers which are released from the mannanases or by a combination ofmannanases and α-galactosidase and/or mannan acetyl esterases can befurther degraded to release free maltose by β-mannosidase and/orβ-glucosidase.

Mannanases have been identified in several Bacillus organisms. Forexample, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11, pp.3505-3510 (1990) describes a beta-mannanase derived from Bacillusstearothermophilus in dimer form having molecular weight of 162 kDa andan optimum pH of 5.5-7.5. Mendoza et al., World J. Microbiol. Biotech.,Vol. 10, No. 5, pp. 551-555 (1994) describes a beta-mannanase derivedfrom Bacillus subtilis having a molecular weight of 38 kDa, an optimumactivity at pH 5.0 and 55C and a pI of 4.8. JP-03047076 discloses abeta-mannanase derived from Bacillus sp., having a molecular weight of373 kDa measured by gel filtration, an optimum pH of 8-10 and a pI of5.3-5.4. JP-63056289 describes the production of an alkaline,thermostable beta-mannanase which hydrolyses beta-1,4-D-mannopyranosidebonds of e.g. mannans and produces manno-oligosaccharides. JP-63036774relates to the Bacillus microorganism FERM P-8856 which producesbeta-mannanase and beta-mannosidase at an alkaline pH. JP-08051975discloses alkaline beta-mannanases from alkalophilic Bacillus sp.AM-001. A purified mannanase from Bacillus amyloliquefaciens useful inthe bleaching of pulp and paper and a method of preparation thereof isdisclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such asa glucanase, xylanase or mannanase active at an extreme pH andtemperature. WO 94/25576 discloses an enzyme from Aspergillus aculeatus,CBS 101.43, exhibiting mannanase activity which may be useful fordegradation or modification of plant or algae cell wall material. WO93/24622 discloses a mannanase isolated from Trichoderma reseei usefulfor bleaching lignocellulosic pulps. An hemicellulase capable ofdegrading mannan-containing hemicellulose is described in WO91/18974 anda purified mannanase from Bacillus amyloliquefaciens is described inWO97/11164.

Preferably, the mannanase enzyme will be an alkaline mannanase asdefined below, more preferably, a mannanase originating from a bacterialsource. Especially, the laundry detergent composition of the presentinvention will comprise an alkaline mannanase selected from themannanase from the strain Bacillus agaradhaerens NICMB 40482; themannanase from Bacillus subtilis strain 168, gene yght; the mannanasefrom Bacillus sp. I633 and/or the mannanase from Bacillus sp. AAI12.Most preferred mannanase for the inclusion in the detergent compositionsof the present invention is the mannanase enzyme originating fromBacillus sp. I633 as described in the co-pending Danish patentapplication No. PA 1998 01340.

The terms “alkaline mannanase enzyme” is meant to encompass an enzymehaving an enzymatic activity of at least 10%, preferably at least 25%,more preferably at least 40% of its maximum activity at a given pHranging from 7 to 12, preferably 7.5 to 10.5.

The alkaline mannanase from Bacillus agaradhaerens NICMB 40482 isdescribed in the co-pending U.S. patent application Ser. No. 09/111,256.More specifically, this mannanase is:

i) a polypeptide produced by Bacillus agaradhaerens, NICMB 40482; or

ii) a polypeptide comprising an amino acid sequence as shown inpositions 32-343 of SEQ ID NO:2 as shown in U.S. patent application Ser.No. 09/111,256; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 70% homologous with said polypeptide, or is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polypeptide havingmannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 97 to nucleotide 1029 as shown in U.S. patentapplication Ser. No. 09/111,256;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 70% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 32 to amino acid residue 343 asshown in U.S. patent application Ser. No. 09/111,256;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pSJ1678 comprising the polynucleotide molecule (the DNAsequence) encoding said mannanase has been transformed into a strain ofthe Escherichia coli which was deposited by the inventors according tothe Budapest Treaty on the International Recognition of the Deposit ofMicroorganisms for the Purposes of Patent Procedure at the DeutscheSammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b,D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 underthe deposition number DSM 12180.

A second more preferred enzyme is the mannanase from the Bacillussubtilis strain 168, which is described in the copending U.S. patentapplication Ser. No. 09/095,163. More specifically, this mannanase is:

i) is encoded by the coding part of the DNA sequence shown in SED ID No.5 shown in the U.S. patent application Ser. No. 09/095,163 or ananalogue of said sequence; and/or

ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6shown in the U.S. patent application Ser. No. 09/095,163; or

iii) an analogue of the polypeptide defined in ii) which is at least 70%homologous with said polypeptide, or is derived from said polypeptide bysubstitution, deletion or addition of one or several amino acids, or isimmunologically reactive with a polyclonal antibody raised against saidpolypeptide in purified form.

Also encompassed in the corresponding isolated polypeptide havingmannanase activity selected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ IDNO:5 as shown in the U.S. patent application Ser. No. 09/095,163

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 70% identical to the amino acid sequence ofSEQ ID NO: 6 as shown in the U.S. patent application Ser. No.09/095,163;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

A third more preferred mannanase is described in the co-pending Danishpatent application No. PA 1998 01340. More specifically, this mannanaseis:

i) a polypeptide produced by Bacillus sp. I633;

ii) a polypeptide comprising an amino acid sequence as shown inpositions 33-340 of SEQ ID NO:2 as shown in the Danish application No.PA 1998 01340; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 65% homologous with said polypeptide, is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polynucleotide moleculeselected from the group consisting of:

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 317 to nucleotide 1243 the Danish application No. PA1998 01340;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 65% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 33 to amino acid residue 340 theDanish application No. PA 1998 01340;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM3 comprising the polynucleotide molecule (the DNAsequence) encoding a mannanase of the present invention has beentransformed into a strain of the Escherichia coli which was deposited bythe inventors according to the Budapest Treaty on the InternationalRecognition of the Deposit of Microorganisms for the Purposes of PatentProcedure at the Deutsche Sammlung von Mikroorganismen und ZellkulturenGmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic ofGermany, on 29 May 1998 under the deposition number DSM 12197.

A fourth more preferred mannanase is described in the Danish co-pendingpatent application No. PA 1998 01341. More specifically, this mannanaseis:

i) a polypeptide produced by Bacillus sp. AAI 12;

ii) a polypeptide comprising an amino acid sequence as shown inpositions 25-362 of SEQ ID NO:2 as shown in the Danish application No.PA 1998 01341; or

iii) an analogue of the polypeptide defined in i) or ii) which is atleast 65% homologous with said polypeptide, is derived from saidpolypeptide by substitution, deletion or addition of one or severalamino acids, or is immunologically reactive with a polyclonal antibodyraised against said polypeptide in purified form.

Also encompassed is the corresponding isolated polynucleotide moleculeselected from the group consisting of

(a) polynucleotide molecules encoding a polypeptide having mannanaseactivity and comprising a sequence of nucleotides as shown in SEQ ID NO:1 from nucleotide 225 to nucleotide 1236 as shown in the Danishapplication No. PA 1998 01341;

(b) species homologs of (a);

(c) polynucleotide molecules that encode a polypeptide having mannanaseactivity that is at least 65% identical to the amino acid sequence ofSEQ ID NO: 2 from amino acid residue 25 to amino acid residue 362 asshown in the Danish application No. PA 1998 01341;

(d) molecules complementary to (a), (b) or (c); and

(e) degenerate nucleotide sequences of (a), (b), (c) or (d).

The plasmid pBXM1 comprising the polynucleotide molecule (the DNAsequence) encoding a mannanase of the present invention has beentransformed into a strain of the Escherichia coli which was deposited bythe inventors according to the Budapest Treaty on the InternationalRecognition of the Deposit of Microorganisms for the Purposes of PatentProcedure at the Deutsche Sammlung von Mikroorganismen und ZellkulturenGmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic ofGermany, on 7 Oct. 1998 under the deposition number DSM 12433.

The mannanase, when present, is incorporated into the treatingcompositions of the present invention preferably at a level of from0.0001% to 2%, more preferably from 0.0005% to 0.1%, most preferred from0.001% to 0.02% pure enzyme by weight of the composition.

The compositions of the present invention may also comprise axyloglucanase enzyme. Suitable xyloglucanases for the purpose of thepresent invention are enzymes exhibiting endoglucanase activity specificfor xyloglucan, preferably at a level of from about 0.001% to about 1%,more preferably from about 0.01% to about 0.5%, by weight of thecomposition. As used herein, the term “endoglucanase activity” means thecapability of the enzyme to hydrolyze 1,4-β-D-glycosidic linkagespresent in any cellulosic material, such as cellulose, cellulosederivatives, lichenin, β-D-glucan, or xyloglucan. The endoglucanaseactivity may be determined in accordance with methods known in the art,examples of which are descnrbed in WO 94/14953 and hereinafter. One unitof endoglucanase activity (e.g. CMCU, AVIU, XGU or BGU) is defined asthe production of 1 μmol reducing sugar/min from a glucan substrate, theglucan substrate being, e.g., CMC (CMCU), acid swollen Avicell (AVIU),xyloglucan (XGU) or cereal β-glucan (BGU). The reducing sugars aredetermined as described in WO 94/14953 and hereinafter. The specificactivity of an endoglucanase towards a substrate is defined as units/mgof protein.

Suitable are enzymes exhibiting as its highest activity XGUendoglucanase activity (hereinafter “specific for xyloglucan”), whichenzyme:

i) is encoded by a DNA sequence comprising or included in at least oneof the following partial sequences

(a) ATTCATTTGT GGACAGTGGA C (SEQ ID No: 1)

(b) GTTGATCGCA CATTGAACCA (SEQ ID NO: 2)

(c) ACCCCAGCCG ACCGATTGTC (SEQ ID NO: 3)

(d) CTTCCTTACC TCACCATCAT (SEQ ID NO: 4)

(e) TTAACATCTT TTCACCATGA (SEQ ID NO: 5)

(f) AGCTTTCCCT TCTCTCCCTT (SEQ ID NO: 6)

(g) GCCACCCTGG CTTCCGCTGC CAGCCTCC (SEQ ID NO: 7)

(h) GACAGTAGCA ATCCAGCATT (SEQ ID NO: 8)

(i) AGCATCAGCC GCTTTGTACA (SEQ ID NO: 9)

(j) CCATGAAGTT CACCGTATTG (SEQ ID NO: 10)

(k) GCACTGCTTC TCTCCCAGGT (SEQ ID NO: 11)

(l) GTGGGCGGCC CCTCAGGCAA (SEQ ID NO: 12)

(m) ACGCTCCTCC AATTTTCTCT (SEQ ID NO: 13)

(n) GGCTGGTAG TAATGAGTCT (SEQ ID NO: 14)

(o) GGCGCAGAGT TTGGCCAGGC (SEQ ID NO: 15)

(p) CAACATCCCC GGTGTTCTGG G (SEQ ID NO: 16)

(q) AAAGATTCAT TTGTGGACAG TGGACGTTGA TCGCACATTG AACCAACCCC AGCCGACCGATTGTCCTTCC TTACCTCACC ATCATTTAAC ATCTTCAC CATGAAGCTT TCCCTTCTCTCCCTTGCCAC CCTGGCTTCC GCTGCCAGCC TCCAGCGCCG CACACTTCTG CGGTCAGTGGGATACCGCCA CCGCCGGTGA CTTCACCCTG TACAACGACC TTTGGGGCGA GACGGCCGGCACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACCAGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO:17)

 or

(r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAGGCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTCCCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA GGAGACGCTGTATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATACAATGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ IDNO:18)

 or a sequence homologous thereto encoding a polypeptide specific forxyloglucan with endoglucanase activity,

ii) is immunologically reactive with an antibody raised against a highlypurified endoglucanase encoded by the DNA sequence defined in i) andderived from Aspergillus aculeatus, CBS 101.43, and is specific forxyloglucan.

More specifically, as used herein the term “specific for xyloglucan”means that the endoglucanse enzyme exhibits its highest endoglucanaseactivity on a xyloglucan substrate, and preferably less than 75%activity, more preferably less than 50% activity, most preferably lessthan about 25% activity, on other cellulose-containing substrates suchas carboxymethyl cellulose, cellulose, or other glucans.

Preferably, the specificity of an endoglucanase towards xyloglucan isfurther defined as a relative activity determined as the release ofreducing sugars at optimal conditions obtained by incubation of theenzyme with xyloglucan and the other substrate to be tested,respectively. For instance, the specificity may be defined as thexyloglucan to β-glucan activity (XGU/BGU), xyloglucan to carboxy methylcellulose activity (XGU/CMCU), or xyloglucan to acid swollen Avicellactivity (XGU/AVIU), which is preferably greater than about 50, such as75, 90 or 100.

The term “derived from” as used herein refers not only to anendoglucanase produced by strain CBS 101.43, but also an endoglucanaseencoded by a DNA sequence isolated from strain CBS 101.43 and producedin a host organism transformed with said DNA sequence. The term“homologue” as used herein indicates a polypeptide encoded by DNA whichhybridizes to the same probe as the DNA coding for an endoglucanaseenzyme specific for xyloglucan under certain specified conditions (suchas presoaking in 5×SSC and prehybridizing for 1 h at −40° C. in asolution of 5×SSC, 5×Denhardt's solution, and 50 μg of denaturedsonicated calf thymus DNA, followed by hybridization in the samesolution supplemented with 50 μCi 32-P-dCTP labeled probe for 18 h at−40° C. and washing three times in 2×SSC, 0.2% SDS at 40° C. for 30minutes). More specifically, the term is intended to refer to a DNAsequence which is at least 70% homologous to any of the sequences shownabove encoding an endoglucanase specific for xyloglucan, including atleast 75%, at least 80%, at least 85%, at least 90% or even at least 95%with any of the sequences shown above. The term is intended to includemodifications of any of the DNA sequences shown above, such asnucleotide substitutions which do not give rise to another amino acidsequence of the polypeptide encoded by the sequence, but whichcorrespond to the codon usage of the host organism into which a DNAconstruct comprising any of the DNA sequences is introduced ornucleotide substitutions which do give rise to a different amino acidsequence and therefore, possibly, a different amino acid sequence andtherefore, possibly, a different protein structure which might give riseto an endoglucanase mutant with different properties than the nativeenzyme. Other examples of possible modifications are insertion of one ormore nucleotides into the sequence, addition of one or more nucleotidesat either end of the sequence, or deletion of one or more nucleotides ateither end or within the sequence.

Endoglucanase specific for xyloglucan useful in the present inventionpreferably is one which has a XGU/BGU, XGU/CMU and/or XGU/AVIU ratio (asdefined above) of more than 50, such as 75, 90 or 100.

Furthermore, the endoglucanase specific for xyloglucan is preferablysubstantially devoid of activity towards β-glucan and/or exhibits at themost 25% such as at the most 10% or about 5%, activity towardscarboxymethyl cellulose and/or Avicell when the activity towardsxyloglucan is 100%. In addition, endoglucanase specific for xyloglucanof the invention is preferably substantially devoid of transferaseactivity, an activity which has been observed for most endoglucanasesspecific for xyloglucan of plant origin.

Endoglucanase specific for xyloglucan may be obtained from the fungalspecies A. aculeatus, as described in WO 94/14953. Microbialendoglucanases specific for xyloglucan has also been described in WO94/14953. Endoglucanases specific for xyloglucan from plants have beendescribed, but these enzymes have transferase activity and thereforemust be considered inferior to microbial endoglucanses specific forxyloglucan whenever extensive degradation of xyloglucan is desirable. Anadditional advantage of a microbial enzyme is that it, in general, maybe produced in higher amounts in a microbial host, than enzymes of otherorigins.

The xyloglucanase, when present, is incorporated into the treatingcompositions of the invention preferably at a level of from 0.0001% to2%, more preferably from 0.0005% to 0.1%, most preferred from 0.001% to0.02% pure enzyme by weight of the composition.

The above-mentioned enzymes may be of any suitable origin, such asvegetable, animal, bacterial, fungal and yeast origin. Purified ornon-purified forms of these enzymes may be used. Also included bydefinition, are mutants of native enzymes. Mutants can be obtained e.g.by protein and/or genetic engineering, chemical and/or physicalmodifications of native enzymes. Common practice as well is theexpression of the enzyme via host organisms in which the geneticmaterial responsible for the production of the enzyme has been cloned.

Said enzymes are normally incorporated in the bleach system at levelsfrom 0.0001% to 2% of active enzyme by weight of the bleach system. Theenzymes can be added as separate single ingredients (prills, granulates,stabilized liquids, etc. containing one enzyme) or as mixtures of two ormore enzymes (e.g. cogranulates).

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers. Examples of such enzyme oxidation scavengers areethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation intosynthetic bleach systems is also disclosed in WO 93/07263 and WO93/07260 to Genencor International, WO 89/08694 to Novo, and U.S. Pat.No. 3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and inU.S. Pat. No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials usefulfor liquid detergent formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr.14, 1981.

Enzyme Stabilizers

Enzymes for use in detergents can be stabilized by various techniques.Enzyme stabilization techniques are disclosed and exemplified in U.S.Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP 199,405 and EP200,586, Oct. 29, 1986, Venegas. Enzyme stabilization systems are alsodescribed, for example, in U.S. Pat. No. 3,519,570. A useful Bacillus,sp. AC13 giving proteases, xylanases and cellulases, is described in WO9401532 to Novo. The enzymes employed herein can be stabilized by thepresence of water-soluble sources of calcium and/or magnesium ions inthe finished compositions which provide such ions to the enzymes.Suitable enzyme stabilizers and levels of use are described in U.S. Pat.No. 5,576,282.

Other Detergent Ingedients

The bleach systems herein may also optionally contain one or more of thefollowing: polymeric dispersing agents, clay soilremoval/anti-redeposition agents, brighteners, suds suppressors, dyes,perfumes, structure elasticizing agents, fabric softeners, carriers,hydrotropes, processing aids and/or pigments. Suitable examples of suchother detergent ingredients and levels of use are found in U.S. Pat. No.5,576,282.

Methods of Cleaning

In addition to the methods for cleaning fabrics, dishes and other hardsurfaces, and body parts by personal cleansing, described herein, theinvention herein also encompasses a laundering pretreatment process forfabrics which have been soiled or stained comprising directly contactingsaid stains and/or soils with a highly concentrated form of the bleachsystem set forth above prior to washing such fabrics using conventionalaqueous washing solutions. Preferably, the bleach system remains incontact with the soil/stain for a period of from about 30 seconds to 24hours prior to washing the pretreated soiled/stained substrate inconventional manner. More preferably, pretreatment times will range fromabout 1 to 180 minutes.

The following examples are meant to exemplify compositions of thepresent invention, but are not necessarily meant to limit or otherwisedefine the scope of the invention.

In the following examples some abbreviations known to those of ordinaryskill in the art are used, consistent with the disclosure set forthherein.

EXAMPLE I

Bleaching detergent compositions having the form of granular laundrydetergents are exemplified by the following formulations.

A B C D E Organic Catalyst* 0.034 0.06 0.03 0.10 0.05 ConventionalActivator 2.00 2.80 2.00 1.80 5.30 (NOBS) Conventional Activator 0.000.00 0.60 0.00 0.00 (TAED) Sodium Percarbonate 5.30 0.00 0.00 4.00 0.00Sodium Perborate 0.00 5.30 3.60 0.00 4.30 Monohydrate Linear 12.00 0.0012.00 0.00 21.00 Alkylbenzenesulfonate C45AE0.6S 0.00 15.00 0.00 15.000.00 C2 Dimethylamine 0.00 2.00 0.00 2.00 0.00 N-Oxide C12 CocoAmidopropyl 1.50 0.00 1.50 0.00 0.00 Betaine Palm N-Methyl 1.70 2.001.70 2.00 0.00 Glucamide C12 1.50 0.00 1.50 0.00 0.00Dimethylhydroxyethyl- ammonium Chloride AE23-6.5T 2.50 3.50 2.50 3.501.00 C25E3S 4.00 0.00 4.00 0.00 0.00 Sodium 25.00 25.00 15.00 15.0025.00 Tripolyphosphate Acrylic Acid/Maleic 0.00 0.00 0.00 0.00 1.00 AcidCopolymer Polyacrylic Acid, 3.00 3.00 3.00 3.00 0.00 partiallyneutralized Soil Release Agent 0.00 0.00 0.50 0.40 0.00Carboxymethylcellulose 0.40 0.40 0.40 0.40 0.40 Sodium Carbonate 2.002.00 2.00 0.00 8.00 Sodium Silicate 3.00 3.00 3.00 3.00 6.00 SodiumBicarbonate 5.00 5.00 5.00 5.00 5.00 Savinase (4T) 1.00 1.00 1.00 1.000.60 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.120.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15Diethylenetriaminepenta 1.60 1.60 1.60 1.60 0.40 (methylenephosphonicAcid) Brightener 0.20 0.20 0.20 0.05 0.20 Sulfonated Zinc 0.50 0.00 0.250.00 0.00 Phthalocyanine Photobleach MgSO₄ 2.20 2.20 2.20 2.20 0.64Na₂SO₄ balance balance balance balance balance *Organic catalyst can beany of the zwitterionic organic catalysts described herein, preferablyit is an iminium-based organic catalyst, more preferably it is adihydroisoquinolinium-based organic catalyst.

Any of the above compositions can be used to launder fabrics at aconcentration of 3500 ppm in water, 25° C., and a 15:1 water:clothratio. The typical pH is about 9.5 but can be can be adjusted byaltering the proportion of acid to Na− salt form ofalkylbenzenesulfonate.

EXAMPLE II

Bleaching detergent compositions having the form of granular laundrydetergents are exemplified by the following formulations.

A B C D E Organic Catalyst* 0.009 0.04 0.14 0.14 0.002 ConventionalActivator 1.80 0.00 0.00 1.00 1.00 (NOBS) Conventional Activator 0.001.00 2.50 3.00 0.00 (TAED) Sodium Percarbonate 5.30 0.00 0.00 0.00 0.00Sodium Perborate 0.00 9.00 17.60 9.00 9.00 Monohydrate Linear 21.0012.00 0.00 12.00 12.00 Alkylbenzenesulfonate C45AE0.6S 0.00 0.00 15.000.00 0.00 C2 Dimethylamine 0.00 0.00 2.00 0.00 0.00 N-Oxide C12 CocoAmidopropyl 0.00 1.50 0.00 1.50 1.50 Betaine Palm N-Methyl 0.00 1.702.00 1.70 1.70 Glucamide C12 1.00 1.50 0.00 1.50 1.50Dimethylhydroxyethyl- ammonium Chloride AE23-6.5T 0.00 2.50 3.50 2.502.50 C25E3S 0.00 4.00 0.00 4.00 4.00 Sodium 25.00 15.00 25.00 15.0015.00 Tripolyphosphate Polyacrylic Acid, 0.00 3.00 3.00 3.00 3.00partially neutralized Soil Release Agent 0.30 0.50 0.50 0.50 0.50Carboxymethylcellulose 0.00 0.40 0.40 0.40 0.40 Sodium Carbonate 0.002.00 2.00 2.00 2.00 Sodium Silicate 6.00 3.00 3.00 3.00 3.00 SodiumBicarbonate 2.00 5.00 5.00 5.00 5.00 Savinase (4T) 0.60 1.00 1.00 1.001.00 Termamyl (60T) 0.40 0.40 0.40 0.40 0.40 Lipolase (100T) 0.12 0.120.12 0.12 0.12 Carezyme (5T) 0.15 0.15 0.15 0.15 0.15Diethylenetriaminepenta 0.40 0.00 1.60 0.00 0.00 (methylenephosphonicAcid) Brightener 0.20 0.30 0.20 0.30 0.30 Sulfonated Zinc 0.25 0.00 0.000.00 0.00 Phthalocyanine Photobleach MgSO₄ 0.64 0.00 2.20 0.00 0.00Na₂SO₄ balance balance balance balance balance *Organic catalyst can beany of the zwitterionic organic catalysts described herein, preferablyit is an iminium-based organic catalyst, more preferably it is adihydroisoquinolinium-based organic catalyst.

Any of the above compositions can be used to launder fabrics at aconcentration of 3500 ppm in water, 25° C., and a 15:1 water:clothratio. The typical pH is about 9.5 but can be can be adjusted byaltering the proportion of acid to Na− salt form ofalkylbenzenesulfonate.

EXAMPLE III

A bleaching detergent powder in accordance with the present inventioncomprises the following ingredients:

Component Weight % Organic Catalyst* 0.01 NOBS 2.0 Sodium PerborateTetrahydrate 10 C₁₂ linear alkyl benzene sulfonate 8 Phosphate (assodium tripolyphosphate) 9 Sodium carbonate 20 Talc 15 Brightener,perfume 0.3 Sodium Chloride 25 Water and Minors Balance to 100% *Organiccatalyst can be any of the zwitterionic organic catalysts describedherein, preferably it is an iminium-based organic catalyst, morepreferably it is a dihydroisoquinolinium-based organic catalyst.

EXAMPLE IV

A laundry bar suitable for hand-washing soiled fabrics is prepared bystandard extrusion processes and comprises the following:

Component Weight % Organic Catalyst* 0.02 NOBS 1.7 TAED 0.2 SodiumPerborate Tetrahydrate 12 C₁₂ linear alkyl benzene sulfonate 30Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodiumpyrophosphate 7 Coconut monoethyanolamide 2 Zeolite A (0.1-10 micron) 5Carboxymethylcellulose 0.2 Polyacrylate (m.w. 1400) 0.2 Brightener,perfume 0.2 Protease 0.3 CaSO₄ 1 MgSO₄ 1 Water 4 Filler² Balance to 100%*Organic catalyst can be any of the zwitterionic organic catalystsdescribed herein, preferably it is an iminium-based organic catalyst,more preferably it is a dihydroisoquinolinium-based organic catalyst.²Can be selected from convenient materials such as CaCO₃, talc, clay,silicates, and the like. Acidic fillers can be used to reduce pH.

Acidic fillers can be used to reduce pH.

EXAMPLE V

A laundry detergent composition suitable for machine use is prepared bystandard methods and comprises the following composition:

Component Weight % Organic Catalyst* 0.3 TAED 10.0 Sodium PerborateTetrahydrate 9.2 Sodium Carbonate 23.74 Anionic surfactant 14.80 AluminoSilicate 21.30 Silicate 1.85 Diethylenetriaminepentacetic acid 0.43Polyacrylic acid 2.72 Brightener 0.23 Polyethylene glycol solids 1.05Sulfate 8.21 Perfume 0.25 Processing aid 0.10 Miscellaneous 0.43 WaterBalance *Organic catalyst can be any of the zwitterionic organiccatalysts described herein, preferably it is an iminium-based organiccatalyst, more preferably it is a dihydroisoquinolinium-based organiccatalyst.

The composition can be used to launder fabrics at a concentration insolution of about 1000 ppm at a temperature of 20-40° C. and a water tofabric ratio of about 20:1.

EXAMPLE VI

Component Weight % Organic Catalyst* 0.082 NOBS 7.20 Sodium PerborateTetrahydrate 8.0 Sodium Carbonate 21.0 Anionic surfactant 12.0 AluminoSilicate 18.0 Diethylenetriaminepentacetic acid 0.3 Nonionic surfactant0.5 Polyacrylic acid 2.0 Brightener 0.3 Sulfate 17.0 Perfume 0.25Miscellaneous 2.95 Water Balance *Organic catalyst can be any of thezwitterionic organic catalysts described herein, preferably it is animinium-based organic catalyst, more preferably it is adihydroisoquinolinium-based organic catalyst.

The composition can be used as a laundry auxiliary for launderingfabrics at a concentration in solution of about 850 ppm at a temperatureof 5-50° C. and a water to fabric ratio of about 20:1.

EXAMPLE VII

A bleaching composition suitable for use in high suds phosphategeographies has the formula:

Component A (% wt) B (% wt) Organic Catalyst* 0.02 0.018 NOBS 1.90 2.00Sodium Perborate Tetrahydrate 2.25 3.00 Sodium Carbonate 13.00 13.00Anionic surfactant 19.00 19.00 Cationic surfactant 0.60 0.60 Nonionicsurfactant — 0.40 Sodium Tripolyphosphate 22.50 22.50Diethylenetriaminepentacetic acid 0.90 0.90 Acrylic acid/Maleic acidcopolymer 0.90 0.90 Carboxymethylcellulose 0.40 0.40 Protease 0.70 0.70Amylase 0.36 0.36 Cellulase 0.35 0.35 Brightener 0.16 0.18 Magnesiumsulfate 0.70 0.70 Water 3.0 1.0 Sodium sulfate Balance Balance *Organiccatalyst can be any of the zwitterionic organic catalysts describedherein, preferably it is an iminium-based organic catalyst, morepreferably it is a dihydroisoquinolinium-based organic catalyst.

While particular embodiments of the subject invention have beendescribed, it will be obvious to those skilled in the art that variouschanges and modifications of the subject invention can be made withoutdeparting from the spirit and scope of the invention. It is intended tocover, in the appended claims, all such modifications that are withinthe scope of the invention.

The compositions of the present invention can be suitably prepared byany process chosen by the formulator, non-limiting examples of which aredescribed in U.S. Pat. Nos. 5,691,297; 5,574,005; 5,569,645; 5,565,422;5,516,448; 5,489,392; and 5,486,303.

In addition to the above examples, the bleach systems of the presentinvention can be formulated into any suitable laundry detergentcomposition, non-limiting examples of which are described in U.S. Pat.Nos. 5,679,630; 5,565,145; 5,478,489; 5,470,507; 5,466,802; 5,460,752;5,458,810; 5,458,809; and 5,288,431.

Having described the invention in detail with reference to preferredembodiments and the examples, it will be clear to those skilled in theart that various changes and modifications may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification.

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What is claimed is:
 1. A bleach system for laundering fabrics in need ofcleaning comprising from about 0.001 ppm to about 5 ppm of azwitterionic organic catalyst compound which is arylimirium zwitterions,which have a net charge of from about +3 to about −3, that arerepresented by the formula [II]:

where R⁵-R⁷ are independently selected from substituted or unsubstitutedradicals selected from the group consisting of H, alkyl, cycloalkyl,aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; alsopresent in this formula is the radical represented by the formula:—T_(o)—Z_(p) ^(⊖) where Z_(p) ⁻ is covalently bonded to T_(o), and Z_(p)⁻ is selected from the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂⁻ and —OSO₂ ⁻ and p is either 1, 2 or 3; T_(o) is selected from thegroup consisting of substituted or unsubstituted, saturated orunsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclicring.
 2. The bleach system according to claim 1 wherein said bleachsystem further comprises from about 2.0 ppm to about 1200 ppm of one ormore peroxygen source.
 3. The bleach system according to claim 1 whereinsaid bleach system further comprises from about 0.5 ppm to about 300 ppmof one or more peracids.
 4. The bleach system according to claim 1wherein said bleach system further comprises from about 1.0 ppm to about600 ppm of one or more peroxygen compounds.
 5. The bleach systemaccording to claim 2 wherein said peroxygen source is selected from thegroup consisting of: (a) preformed peracid compounds selected from thegroup consisting of percarboxylic acids and salts, percarbonic acids andsalts, perimidic acids and salts, peroxymonosulfuric acids and salts,and mixtures thereof; (b) hydrogen peroxide sources selected from thegroup consisting of perborate compounds, percarbonate compounds,perphosphate compounds and mixtures thereof; and a bleach activator. 6.The bleach system according to claim 1 wherein said zwitterionic organiccatalyst compound is present at a concentration of from about 0.01 ppmto about 3 ppm.
 7. The bleach system according to claim 6 wherein saidzwitterionic organic catalyst compound is present at a concentration offrom about 0.1 ppm to about 2 ppm.
 8. The bleach system according toclaim 7 wherein said zwitterionic organic catalyst compound is presentat a concentration of from about 0.2 ppm to about 1 ppm.
 9. The bleachsystem according to claim 1 wherein said zwitterionic organic catalystcompound is aryliminium zwitterions, which have a net charge of fromabout +3 to about −3, that are represented by the formula [XII]:

where m is 1 to 3 when G is present and m is 1 to 4 when G is notpresent; and n is an integer from 0 to 4; each R²⁶ is independentlyselected from a substituted or unsubstituted radical selected from thegroup consisting of H, alkyl, cycloalkyl, aryl, fused aryl, heterocyclicring, fused heterocyclic ring, nitro, halo, cyano, sulfonato, alkoxy,keto, carboxylic, and carboalkoxy radicals, and any two vicinal R²⁶substituents may combine to form a fused aryl, fused carbocyclic orfused heterocyclic ring; R²⁵ may be a substituted or unsubstitutedradical selected from the group consisting of H, alkyl, cycloalkyl,alkaryl, aryl, aralkyl, heterocyclic ring, silyl, nitro, halo, cyano,sulfonato, alkoxy, keto, carboxylic and carboalkoxy radicals; alsopresent in this formula is the radical represented by the formula:—T_(o)—Z_(p) ^(⊖) where Z_(p) ⁻ is covalently bonded to T_(o), and Z_(p)⁻ is selected from the group consisting of —CO₂ ⁻, —SO₃ ⁻, —OSO₃ ⁻, —SO₂⁻ and —OSO₂ ⁻ and p is either 1, 2 or 3; T_(o) is selected from thegroup consisting of:

wherein q is an integer from 1 to 8; R²⁹ is independently selected fromsubstituted or unsubstituted radicals selected from the group consistingof linear or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl,alkylene, heterocyclic ring, alkoxy, arylcarbonyl, carboxyalkyl andamide groups; G is selected from the group consisting of: (1) —O—; (2)—N(R³⁰)—; and (3) —N(R³⁰R³¹)—; R²⁷, R²⁸, R³⁰ and R³¹ are substituted orunsubstituted radicals independently selected from the group consistingof H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylenes,heterocyclic ring, alkoxys, arylcarbonyl groups, carboxyalkyl groups andamide groups; any of R²⁵, R²⁶, R²⁷, R²⁸, R³⁰ and R³¹ may be joinedtogether with any other of R²⁵, R²⁶, R²⁷, R²⁸, R³⁰ and R³¹ to form partof a common ring; any germinal R²⁷-R²⁸ may combine to form a carbonyl;any vicinal R²⁷-R³¹ may join to form unsaturation; and wherein any onegroup of substituents R²⁷-R³¹ may combine to form a substituted orunsubstituted fused unsaturated moiety.
 10. The bleach system accordingto claim 9 wherein said zwitterionic organic catalyst compound is anaryliminium zwitterion of the formula [XII] wherein R²⁵ is H or methyl,R²⁶ is independently selected from H, alkyl and alkoxy, and for theradical represented by the formula: —T_(o)—Z_(p) ^(⊖) Z_(p) ⁻ is —CO₂ ⁻,—SO₃ ⁻ or —OSO₃ ⁻, and p is 1 or
 2. 11. The bleach system according toclaim 10 wherein said zwitterionic organic catalyst compound is anaryliminium zwitterion of the formula [XII] wherein for the radicalrepresented by the formula: —T_(o)—Z_(p) ^(⊖) Z_(p) ⁻ is —CO₂ ⁻, —SO₃ ⁻or —OSO₃ ⁻, and p is 1, and T_(o) is selected from the group consistingof:

wherein q is an integer from 2 to 4, and each R²⁹ is individually,independently selected from the group consisting of H and linear orbranched C₁-C₁₈ substituted or unsubstituted alkyl and aryl.
 12. Thebleach system according to claim 1 wherein said bleach system furthercomprises a surfactant.
 13. The bleach system according to claim 1wherein said bleach system further comprises an enzyme.
 14. The bleachsystem according to claim 1 wherein said bleach system further comprisesa chelating agent.
 15. The bleach system according to claim 2 whereinsaid peroxygen source and said zwitterionic organic catalyst compoundare present in said bleach system at a molar ratio of greater than 1:1.16. The bleach system of claim 1 made by the process comprising: a)providing a wash solution; and b) adding to said wash solution a bleachcomposition comprising an amount of zwitterionic organic catalystcompound which is aryliminium zwitterions, which have a net charge offrom about +3 to about −3, that are represented by the formula [II]:

 where R⁵-R⁷ are independently selected from substituted orunsubstituted radicals selected from the group consisting of H, alkyl,cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro,halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxyradicals; also present in this formula is the radical represented by theformula: —T_(o)—Z_(p) ^(⊖)  where Z_(p) ⁻ is covalently bonded to T_(o),and Z_(p) ⁻ is selected from the group consisting of —CO₂ ⁻, —SO₃ ⁻,—OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻ and p is either 1, 2 or 3; T_(o) is selectedfrom the group consisting of substituted or unsubstituted, saturated orunsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclicring; such that the resulting concentration of the zwitterionic organiccatalyst compound in said wash solution is from about 0.001 ppm to about5 ppm.
 17. A method for laundering a fabric in need of laundering, saidmethod comprises contacting said fabric with a laundry solution having ableach system according to claim
 1. 18. The method according to claim 17wherein said fabric is a colored fabric.
 19. The method according toclaim 17 wherein said method is carried out in an automatic washingmachine.
 20. A bleach system for laundering fabrics in need of cleaningcomprising a) a peroxygen source; and b) a zwitterionic organic catalystcompound which is aryliminium zwitterions, which have a net charge offrom about +3 to about −3, that are represented by the formula [II]:

 where R⁵-R⁷ are independently selected from substituted orunsubstituted radicals selected from the group consisting of H, alkyl,cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro,halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxyradicals; also present in this formula is the radical represented by theformula: —T_(o)—Z_(p) ^(⊖)  where Z_(p) ⁻ is covalently bonded to T_(o),and Z_(p) ⁻ is selected from the group consisting of —CO₂ ⁻, —SO₃ ⁻,—OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻ and p is either 1, 2 or 3; T_(o) is selectedfrom the group consisting of substituted or unsubstituted, saturated orunsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclicring; wherein said peroxygen source and said zwitterionic organiccatalyst compound are present in said bleach system at a molar ratiogreater than 1:1, said bleach system comprising from about 0.001 ppm toabout 5 ppm of said zwitterionic organic catalyst.
 21. The bleach systemaccording to claim 20 wherein said peroxygen source and saidzwitterionic organic catalyst compound are present in said bleach systemat a molar ratio of from about 30,000:1 to about 10:1.
 22. The bleachsystem according to claim 21 wherein said peroxygen source and saidzwitterionic organic catalyst compound are present in said bleach systemat a molar ratio of from about 10,000:1 to about 50:1.
 23. The bleachsystem according to claim 22 wherein said peroxygen source and saidzwitterionic organic catalyst compound are present in said bleach systemat a molar ratio of from about 5,000:1 to about 100:1.
 24. The bleachsystem according to claim 23 wherein said peroxygen source and saidzwitterionic organic catalyst compound are present in said bleach systemat a molar ratio of from about 3,500:1 to about 150:1.
 25. A bleachsystem for laundering fabrics in need of cleaning comprising a) aperacid; and b) a zwitterionic organic catalyst compound which isaryliminium zwitterions, which have a net charge of from about +3 toabout −3, that are represented by the formula [II]:

 where R⁵-R⁷ are independently selected from substituted orunsubstituted radicals selected from the group consisting of H, alkyl,cycloalkyl, aryl, alkaryl, aralkyl, heterocyclic ring, silyl, nitro,halo, cyano, sulfonato, alkoxy, keto, carboxylic and carboalkoxyradicals; also present in this formula is the radical represented by theformula: —T_(o)—Z_(p) ^(⊖)  where Z_(p) ⁻ is covalently bonded to T_(o),and Z_(p) ⁻ is selected from the group consisting of —CO₂ ⁻, —SO₃ ⁻,—OSO₃ ⁻, —SO₂ ⁻ and —OSO₂ ⁻ and p is either 1, 2 or 3; T_(o) is selectedfrom the group consisting of substituted or unsubstituted, saturated orunsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocyclicring; wherein said peracid and said zwitterionic organic catalystcompound are present in said bleach system at a molar ratio greater than1:1, said bleach system comprising from about 0.001 ppm to about 5 ppmof said zwitterionic organic catalyst.